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AOC II – Docket No. V-W-’04-C-784 – SSC WP May 2015

Appendix B

Quality Assurance Project Plan Addendum

AOC II – Docket No. V-W-’04-C-784 – SSC WP Appendix B May 2015

Supplemental Soil Characterization Work Plan

Appendix B Quality Assurance Project Plan Addendum

Pines Area of Investigation AOC II Docket No. V-W-’04-C-784

Revision 3

May 2015

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Quality Assurance Project Plan Addendum Pines Area of Investigation

Section: QAPP Approvals Revision: 3

Date: May 2015 Page: 1 of 1


QAPP Approvals

Quality Assurance Project Plan Addendum Supplemental Soil Characterization Work Plan

Pines Area of Investigation Revision 3

Prepared by: AECOM Prepared for: Brown Inc. and NIPSCO

May ___, 2015 Project Manager Lisa JN Bradley, Haley & Aldrich

Date

May ___, 2015 AECOM Project Quality Assurance Officer Date Debra Simmons

USEPA Region V Remedial Project Manager Date Erik Hardin

USEPA Region V QA Plan Reviewer Date

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Section: Distribution List Revision: 3



Distribution List

Erik Hardin, USEPA Lisa JN Bradley, Haley & Aldrich Valerie Blumenfeld, Brown Inc. Dan Sullivan, NiSource Robert Shoemaker, AECOM Debra L. Simmons, AECOM Janice Jaeger, ALS Rochester Greg Salata, ALS Kelso Edith Kent, General Engineering Laboratories Keith Wagner, RJ Lee Group

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Section: Table of Contents Revision: 3

Date: May 2015 Page: i of iv


Table of Contents

QAPP APPROVALS

DISTRIBUTION LIST

TABLE OF CONTENTS

ACRONYMS

STANDARD CHEMICAL ABBREVIATIONS

DISCLAIMER

A.0 PROJECT MANAGEMENT ................................................................................................ 1

A.1 Introduction .................................................................................................................. 1

A.2 Project Schedule ......................................................................................................... 1

A.3 Distribution List ............................................................................................................ 1

A.4 Project/Task Organization ........................................................................................... 1

A.5 Problem Definition and Background ........................................................................... 2

A.6 Project/Task Description ............................................................................................. 2

A.7 Quality Objectives and Criteria for Measurement Data .............................................. 2

B.0 MEASUREMENT/DATA ACQUISITION ............................................................................ 1

B.1 Sampling Process Design ........................................................................................... 1

B.2 Sampling Methods Requirements ............................................................................... 1

B.2.1 Field Measurements ................................................................................... 1

B.2.2 Sampling Procedures.................................................................................. 1

B.3 Sample Handling and Custody .................................................................................... 1

B.3.1 Sample Containers, Preservation, and Holding Times ............................... 1

B.3.2 Sample Labeling ......................................................................................... 1

B.4 Analytical Methods ...................................................................................................... 1

B.4.1 Laboratory Analytical Procedures ............................................................... 2

B.4.1.1 Metals ........................................................................................... 2

B.4.1.2 Particulate Matter ......................................................................... 2

B.4.1.3 Radionuclides ............................................................................... 3

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B.4.2 List of Project Target Constituents and Detection Limits ............................ 3

B.5 Quality Control............................................................................................................. 3

B.6 Instrument/Equipment Testing, Inspection, and Maintenance .................................... 4

B.6.1 Field Instrument Maintenance .................................................................... 4

B.7 Laboratory Instrument Preventative Maintenance ...................................................... 4

B.8 Instrument/Equipment Calibration and Frequency...................................................... 4

B.8.1 Field Instruments ........................................................................................ 4

B.8.2 Analytical Instrumentation ........................................................................... 4

C.0 PROJECT ASSESSMENT/OVERSIGHT ........................................................................... 1

D.0 DATA VALIDATION AND USABILITY .............................................................................. 1

REFERENCES .................................................................................................................................... 1

ATTACHMENT A Laboratory Standard Operating Procedures

ATTACHMENT B Gamma Spectroscopy Library

ATTACHMENT C Radioisotope Calculation Spreadsheet

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Date: May 2015 Page: iii of iv


List of Tables Table A-1 Sample Summary

Table A-2 Laboratory Parameters by Sample Medium

Table A-3 Target Analytes, Reporting Limits, and Data Quality Levels for Metals

Table A-4 Primary Target Analytes, Reporting Limits, and Data Quality Levels for Radionuclides

Table A-5 Quality Control Performance Criteria for Soil Samples

Table B-1 Summary of Sample Container, Preservation, and Holding Time Requirements for Soil and CCB/Soil Mixture Samples

Table B-2 Analytical Methodologies

Table B-3 Analytical Quality Control Checks

Table B-4 Maintenance Procedures and Schedule for Field Instruments

Table B-5 Maintenance Procedures and Schedule for Analytical Instruments

Table B-6 Laboratory Equipment Monitoring

Table B-7 Field Instrument Calibration

Table B-8 Analytical Instrument Calibration

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List of Figures Figure A-1 Project Organization Chart

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Section: Acronyms Revision: 3



Acronyms

ALS The ALS Group

AOC II Administrative Order on Consent, 2004; Docket No. V-W-’04-C-784

bgs below ground surface

°C degrees Celsius

CAS Chemical Abstracts Service

CCB Coal Combustion By-product

CCBK Continuing Calibration Blank

COC Constituent of Concern

DOE Department of Energy

DQL Data Quality Level

EM Electron Multiplier

EML Environmental Measurements Laboratory

FS Feasibility Study

FWHM Full Width at Half Maximum

GEL General Engineering Laboratory

HASL Health and Safety Laboratory

IC Inductively Coupled

ICBK Initial Calibration Blank

ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy

ICP-MS Inductively Coupled Plasma-Mass Spectrometry

IDL Instrument Detection Limit

keV kiloelectron volt

LCS Laboratory Control Sample

LOI Loss on Ignition

MDC Minimum Detectable Concentration

MDL Method Detection Limit

mg/kg milligram per kilogram

mL milliliter

MRL Method Reporting Limit

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MS/MSD Matrix Spike/Matrix Spike Duplicate

NA Not Applicable

NIPSCO Northern Indiana Public Service Company

NIST National Institute of Standards and Technology

NORM Naturally Occurring Radioactive Material

ORP Oxidation-Reduction Potential

oz ounce

pCi/g Picocuries per gram

PLM polarized light microscopy

PRG Preliminary Remediation Goal

QA Quality Assurance

QAPP Quality Assurance Project Plan

QC Quality Control

%R Percent Recovery

RI Remedial Investigation

RI/FS Remedial Investigation and Feasibility Study

RJ Lee RJ Lee Group

RL Reporting Limit

RPD Relative Percent Difference

RSD Relative Standard Deviation

RSL Regional Screening Level

SOP Standard Operating Procedure

SOW Statement of Work

SR Sample Result

SSC Supplemental Soil Characterization

TOC Total Organic Carbon

ug/L micrograms per liter

USEPA United States Environmental Protection Agency

XRD X-Ray Diffraction

XRF X-Ray Fluorescence

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Section: Standard Chemical Abbreviations Revision: 3



Standard Chemical Abbreviations

Ac Actinium

Al Aluminum

Am Americium

As Arsenic

Ba Barium

Be Beryllium

Bi- Bismuth

Co Cobalt

Cs Cesium

Cr Chromium

Fe Iron

K Potassium

Pa Protactinium

Pb Lead

Ra Radium

Th Thorium

Tl Thallium

U Uranium

V Vanadium

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Section: Disclaimer Revision: 3



Disclaimer

This document is a draft document prepared under a federal administrative order on consent. This document has not undergone formal review by U.S. Environmental Protection Agency (USEPA), however, this document has incorporated comments provided by USEPA on the previous draft version of the report (see Appendix D of the Supplemental Soil Characterization (SSC) Work Plan). The opinions, findings, and conclusions expressed are those of the author and not necessarily those of USEPA.

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Section: Section A Revision: 3



A.0 Project Management

A.1 Introduction In April 2004, the United States Environmental Protection Agency (USEPA) and the Respondents (Brown Inc., Ddalt Corp., Bulk Transport Corp., and Northern Indiana Public Service Company (NIPSCO)) signed an Administrative Order on Consent (AOC II) (Docket No. V-W-’04-C-784) to conduct a Remedial Investigation and Feasibility Study (RI/FS) at the Pines Area of Investigation, located in the environs of the Town of Pines, Indiana, as set forth in Exhibit I to II (AOC II, 2004). AOC II (Section VII. 22) and its attachment, the Statement of Work (SOW) (Task 8), require the Respondents to conduct a Feasibility Study (FS) as part of the RI/FS process. As documented in the FS (AECOM, 2014a), additional soil investigations will be conducted. A Supplemental Soil Characterization (SSC) Work Plan (AECOM, 2014b) provides the details for conducting this work.

This Quality Assurance Project Plan (QAPP) Addendum incorporates the RI/FS QAPP (ENSR [now AECOM], 2005, as revised in 2008) by reference and was prepared to reflect the scope of work described in the SSC Work Plan, and is provided as Appendix B of the SSC Work Plan.

A.2 Project Schedule The project schedule for the initial nine properties sampled (Appendix G of the SSC Work Plan) is presented in Section 6.0 of the SSC Work Plan.

The schedule for sampling the remaining properties (Appendix H of the SSC Work Plan) will consist of the same components as outlined in Section 6.0 of the SSC Work Plan. Access agreements to conduct work on private properties have been submitted to property owners and the majority of the agreements have been signed and received. The Respondents will continue to work cooperatively with USEPA to obtain the remaining access agreements. Field work is tentatively scheduled to commence May 18, 2015 and is expected to be completed within approximately four weeks; however, delays in receiving any of the remaining access agreements may extend this schedule. Once the field activities are completed, compilation of field notes, laboratory analysis and other report preparation tasks continue for another 10 weeks. Note that expedited laboratory turn-around times (5 business days following sample receipt) have been requested and data maps/tables for each property will be provided to USEPA within one week following receipt of the validated data package for each property.

A.3 Distribution List The QAPP Addendum, and any subsequent revisions, will be distributed to the personnel shown on the Distribution List that immediately follows the approval page.

A.4 Project/Task Organization The lines of authority and communication specific to the Quality Assurance (QA) program for this additional soil investigation are presented in Figure A-1.

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Section: Section A Revision: 3



A.5 Problem Definition and Background Background and the objectives specific to the additional soil investigation are provided in Sections 1.1 and 1.2, respectively, of the SSC Work Plan. Additional background information is provided in Appendix H of the SSC Work Plan.

A.6 Project/Task Description To meet the objectives defined in the SSC Work Plan, three data collection tasks will be conducted:

1. Gamma count rate and gamma dose rate surveys. 2. Coal combustion by-product (CCB) visual inspection confirmation sampling. 3. Soil sampling of selected properties for specific constituents; constituents are specific to the individual

sampling tasks, as outlined in Appendix G and Appendix H of the SSC Work Plan.

The number of field and quality control (QC) samples that will be collected for each analytical parameter is presented in Table A-1. A summary of analytical parameters by medium is presented in Table A-2. Target compounds and analytical parameters for all matrices are presented with their respective laboratory detection limits and data quality levels (DQLs) in Tables A-3 (Metals) and A-4 (primary radionuclide target analytes), and in Attachment B (gamma spectroscopy library).

All data generated from field activities or from the analytical program will be reviewed through a tiered review process and validated prior to reporting. All of the laboratory data will be validated as described in Section D.0.

A.7 Quality Objectives and Criteria for Measurement Data The objectives for precision, accuracy, and sensitivity are provided in Table A-5.

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Section: Section B Revision: 3



B.0 Measurement/Data Acquisition

B.1 Sampling Process Design The rationale for the sample design is provided in Section 3.0 of the SSC Work Plan for the work identified in Appendix G of the SSC Work Plan.

The rationale for the sample design for the work identified in Appendix H of the SSC Work Plan is provided in that Appendix.

B.2 Sampling Methods Requirements B.2.1 Field Measurements Field measurements associated with the work described in Appendix G will include a gamma walk-over survey and a gamma dose rate survey. These procedures are described in Sections 3.2.1 and 3.2.2 of the SSC Work Plan. Standard operating procedures (SOPs) are included in Appendix C of the SSC Work Plan.

Field measurements associated with the work described in Appendix H consist of screening selected samples with a field-portable X-ray fluorescence analyzer (FP-XRF), the Operating Procedure for which is provided in Appendix H, Attachment 2.

B.2.2 Sampling Procedures The SOPs that will be utilized for CCB visual inspection, confirmation sampling, and private property soil sampling (Sections 3.3 and 3.4 of the SSC Work Plan, respectively) are provided in Appendix C of the SSC Work Plan.

An updated procedure for conducting visual inspections associated with the work described in Appendix H is provided in Appendix H, Attachment 2.

B.3 Sample Handling and Custody B.3.1 Sample Containers, Preservation, and Holding Times A summary of sample container, preservation, and holding time requirements is presented in Table B-1.

B.3.2 Sample Labeling For the work described in Appendix G, labeling of sample containers is described in Section 4.2.2.2 of the SSC Work Plan and Section 8 of Appendix G. For the work described in Appendix H, labeling of containers is described in Section 7 of Appendix H.

B.4 Analytical Methods Analyses will be performed by laboratories that have been utilized for previous investigations at the Pines Area of Investigation and approved by USEPA. Chemical analyses of soil samples for metals for the scope in Appendix G (including hexavalent chromium), except total uranium will be performed by The ALS Group ([ALS]; formerly

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Columbia Analytical Services, Inc.) in Rochester, NY. Gamma spectroscopy analyses for the radioisotopes and inductively coupled plasma – mass spectroscopy (ICP-MS) for total uranium (calculated from U-235 and U-238) will be performed by General Engineering Laboratories, LLC (GEL) in Charleston, SC. Particulate matter analyses will be performed by RJ Lee Group (RJ Lee) in Monroeville, PA.

Chemical analyses of soil samples for metals for the Appendix H sampling will be performed by ALS in Kelso, WA.

B.4.1 Laboratory Analytical Procedures

B.4.1.1 Metals

A list of the ALS and GEL SOPs for metals analyses is provided in Table B-2. The SOPs are included in Attachment A.

B.4.1.2 Particulate Matter

The particulate matter analysis by RJ Lee will consist of polarized light microscopy (PLM), X-ray diffraction (XRD), X-ray fluorescence (XRF), and loss on ignition (LOI). The PLM analysis will be used to identify crystalline and non-crystalline glassy and organic phases in the sample and to identify particles with fly ash or bottom ash morphologies. The PLM analyses will be performed in general accordance to EPA 600/R‐93/116, Test Method for the Determination of Asbestos in Bulk Building Materials. The SOPs for the particulate matter analysis are not included in Attachment A because RJ Lee considers them to be proprietary. The SOPs are available for review at the RJ Lee facility. A summary of the procedures are presented below.

The sample will be spread on a grid on one or more glass slides, and 400 random points on that grid are observed. Particles will be identified by the microscopist as either fly ash or bottom ash and these particles will be counted. If one particle of fly ash is counted in any of those 400 grid squares, the sample will be reported as containing 0.25% fly ash. If a single fly ash article is observed in the light microscopy field, but it is not contained in any of the 400 grid squares randomly selected for counting, a result of “trace” will be reported, which quantitatively is <0.25% fly ash. The same method will apply to the bottom ash results.

Particle Counting Interpretations Observations on a 400-point Grid

Result Observations on a 400-point Grid ND No particles observed within or outside of the grid <0.25% No particles observed within the grid, but particle(s) observed upon review of the

entire slide 0.25% 1 particle observed within the grid 0.5% 2 particles observed 0.75% 3 1% 4 1.5% 6 2% 8

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The XRD analysis will be used to identify the crystalline phases present in the samples and will be performed in general accordance to ASTM D934, Standard Practices for Identification of Crystalline Compounds in Water-Formed Deposits by X-ray Diffraction. The LOI analysis (based on ASTM D7348, Standard Test Methods for Loss on Ignition (LOI) of Solid Combustion Residues) will be used to determine the weight of percent organic and volatile constituents in the sample and to prepare the samples for XRF analysis by removing the carbonaceous material, carbon dioxide, and water content. The XRF analysis will be used to determine the elemental composition of the residual material in the sample. XRF will be performed in general accordance to ASTM D4326, Standard Method for Analysis of Coal and Coal Ash by X-ray Fluorescence.

B.4.1.3 Radionuclides

A list of the GEL SOPs is provided in Table B-2. The SOPs are included in Attachment A.

For the radionuclides by gamma spectroscopy, GEL will dry and prep samples according to their SOPs and seal samples in a 100 cc “tuna can” sample container for a minimum of 28-days prior to analyses. The samples will be counted using the more sensitive detector (N-type) and will be counted for a sufficient amount of time, to a maximum count time of 1000 minutes, in order to meet the minimum detectable concentration (MDC) requirements in Table A-4. The laboratory gamma spectroscopy library includes those isotopes that are used to directly or indirectly quantify the primary radionuclide target analytes. These isotopes are also listed in Table A-4 as primary target analytes with MDCs. Due to the parent/progeny relationship with the isotopes in the gamma spectroscopy library and Table A-4, MDCs are not established for all isotopes on the library list. MDCs in Table A-4 establish the detection limits for the primary radionuclide target analytes. The radionuclides that will be reported for the soil samples will be based on the gamma spectroscopy library that is provided in Attachment B.

The following limits on sensitivity parameters will be applied for gamma spectroscopy analysis:

• Energy Tolerance: 1.5 kiloelectron volts (keV) • Peak Sensitivity: 3.0 • Abundance Limit: 75%

GEL will conduct a thorough review of 'Unidentified Peaks' and note such peaks with comments in the batch narrative. Any nuclides identified in the 'Unidentified Peaks' report that are not already being reported may be added to the library following approval by the AECOM project manager. For each radionuclide in the gamma library, GEL will report the concentration along with its sample specific uncertainty for each sample as obtained during analysis even if the concentration is less than the MDC or is negative (Section 16.6 in MARLAP, 2004).

USEPA plans to collect split samples for independent analysis. The specific procedures for sample selection, collection, and shipment will be provided by USEPA and will be accommodated in the field.

B.4.2 List of Project Target Constituents and Detection Limits A listing of project target constituents and reporting limits (RLs) or MDCs for each analyte group listed in Table B-2 can be found in Tables A-3 (metals) and A-4 (primary radionuclide target analytes) and in Attachment B (gamma spectroscopy library).

B.5 Quality Control Table B-3 summarizes the QC for the analytical methods. Field QC will include field duplicates, equipment blanks, and matrix spike/matrix spike duplicate (MS/MSD) samples, as appropriate for the analytical method. Table A-5

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presents the limits for each field QC sample. Procedures and frequencies will be consistent with those described in the RI/FS QAPP.

B.6 Instrument/Equipment Testing, Inspection, and Maintenance B.6.1 Field Instrument Maintenance The maintenance schedule and trouble-shooting procedures for field instrument are indicated in Table B-4.

B.7 Laboratory Instrument Preventative Maintenance Table B-5 provides the frequency with which components of key analytical instruments will be serviced. Table B-6 provides a summary of the monitoring of laboratory equipment.

B.8 Instrument/Equipment Calibration and Frequency B.8.1 Field Instruments Calibration of field instruments will be performed according to the manufacturer’s instructions and the SOPs included in Appendix C of the SSC Work Plan. A summary of calibration procedures and frequencies is provided as Table B-7.

B.8.2 Analytical Instrumentation The SOP for each analysis performed in the laboratory describes the calibration procedures, their frequency, acceptance criteria, and the conditions that will require recalibration. This information is summarized in Table B-8. The SOPs are included as Attachment A.

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Section: Section C Revision: 3



C.0 Project Assessment/Oversight

No audits of field activities or the laboratory analyses associated with the investigation to be conducted under the SSC Work Plan are planned.

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Section: Section D Revision: 3



D.0 Data Validation and Usability

All chemical and radiochemical data generated as part of the Appendix G scope of work will be subjected to limited validation. Ten percent of the data associated with the Appendix H scope of work will be subjected to full data validation; the remaining chemical data will be subjected to limited validation. Validation of the laboratory data associated with the Appendix H scope of work will be performed by Environmental Standards, Inc. The elements of full and limited validated are described in the RI/FS QAPP (ENSR, 2008). Consistent with the RI/FS QAPP, all metals and radionuclide data packages will be submitted by the laboratories as Level IV data deliverables in the event that a more thorough data validation is required at a later date.

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Section: References Revision: 3



References

AECOM. 2014a. Feasibility Study. Pines Area of Investigation. July 2014.

AECOM. 2014b. Supplemental Soil Characterization Work Plan. Pines Area of Investigation. November 2014.

ENSR. 2005. Remedial Investigation/Feasibility Study Work Plan, Volumes 1-7. September 16, 2005.

ENSR. 2008. Remedial Investigation/Feasibility Study Work Plan, Volume 3, Quality Assurance Project Plan. Revised March 31, 2008.

MARLAP. 2004. Multi-Agency Radiological Laboratory Analytical Protocols Manual. July 2004.

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Section: Tables Revision: 3

Date: May 2015


Tables

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Date: May 2015


Table A-1 Sample Summary

Matrix Number of Locations

(Samples) Field

Parameters Analytical

Parameters Equipment

Blanks1 Field

Duplicates2 MS/

MSDs2,3

Soil (Quadrant Sampling

Associated with

Appendix G of the

SSC Work Plan)

• 9 properties • 4 quadrants per property4

(up to 7 quadrants if special uses)

• 1 composite (from 5 locations) per quadrant

• 3 depths5: 0 - 6 inches below ground surface (bgs), 6 -18 inches bgs, and 1.5 - 5 feet bgs.

Total samples: 72 - 189

None Aluminum Arsenic Chromium (total) Hexavalent Chromium Cobalt Iron Thallium Total uranium Vanadium Radionuclides6

9 9 9 pairs


Associated with

Appendix H of the SSC Work Plan)

37 Identified Properties • 4 quadrants per

property4 (up to 7 quadrants if special uses)

• 1 composite (from 5 locations) per quadrant

• 2 to 3 depths: o 0 - 6 inches bgs, o 6 -18 inches bgs, and o 18-36 inches bgs7.

• Replicate (triplicate) sampling at 15% of Quadrants

None Arsenic

Lead

Thallium

37-74 37 37

32 Additional Properties • 4 quadrants per

property4 (up to 7 quadrants if special uses)

• 1 composite per property, if no CCBs are observed, plus

• 1 composite per property if CCBs are observed along the road

• 1 depth: 0 - 6 inches bgs

None Arsenic

Lead

Thallium

2-4 4

4

Total samples: 420 – 1,075

39-78 41 41

Soil/CCB Mixture (CCB VI Verification Sampling)

15 None Particulate matter (PLM, XRF, XRD, LOI)

NA 0 NA

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Date: May 2015


Matrix Number of Locations

(Samples) Field

Parameters Analytical

Parameters Equipment

Blanks1 Field

Duplicates2 MS/

MSDs2,3 1 Equipment rinsate blanks will be collected at a minimum frequency of one per property per non-disposable or non-dedicated piece

of equipment used. 2 For Appendix G scope: Collected at a minimum frequency of one per 10 samples submitted for analysis for the CCB/soil mixture

samples, and a frequency of one per property sampled for the soil samples. For Appendix H scope: Collected at a minimum frequency of one per Identified Property and at a minimum frequency of one per 20

samples collected from Additional Properties. 3 Collected at a frequency of one per property sampled, except not applicable to radionuclides. 4 Up to 7 quadrants may be established based on the property size and to address the three specific property uses defined in the

SSC Work Plan: gardens, children’s play areas (based on the presence of swing sets and/or other outdoor play equipment), and unpaved driveways where CCBs are observed.

5 Samples collected at the 1.5 - 5 foot horizon will be submitted for analysis only if CCBs are visually observed in at least 1 of the 5 samples to be composited from a single quadrant.

6 Refer to Table A-4 and Attachment B (gamma spectroscopy library) for the specific list of radionuclides. 7 Samples collected from the 18-36 inch horizon will be submitted for analysis if all or a portion of the 18-to-36-inch interval contains

no visual evidence of CCBs in at least 1 of the five samples in a quadrant; samples with no visually-observed CCBs will be composited from a single quadrant.

bgs – below ground surface CCB – Coal Combustion By-product LOI – Loss on Ignition NA – Not Applicable MS/MSD – Matrix Spike/Matrix Spike Duplicate PLM – Polarized Light Microscopy SSC – Supplemental Soil Characterization XRF – X-ray Fluorescence XRD –X-ray Diffraction

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Table A-2 Laboratory Parameters by Sample Medium

Parameter Soil4

(Quadrant Sampling – Appendix G)


– Appendix H)

Soil/CCB Mixtures4 (CCB VI Verification

Sampling) Metals1 X X Hexavalent chromium X Percent moisture X Radionuclides2 X Particulate matter3 X 1 Refer to Table A-3 for the specific list of analytes. 2 Refer to Table A-4 and Attachment B (gamma spectroscopy library) for the specific list of radionuclides. 3 PLM, XRF, XRD, LOI 4 Note that particulate matter analyses will be conducted on samples collected from locations where CCBs were previously

identified to be present. CCBs may also be present in the soil samples identified for collection in Table A-1, however, those samples will be collected without biasing the sample locations based on the presence or absence of CCBs.

CCB – Coal Combustion By-product LOI – Loss on Ignition PLM – Polarized Light Microscopy XRD – X-Ray Diffraction XRF – X-Ray Fluorescence

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Table A-3a Target Analytes, Reporting Limits, and Data Quality Levels for Metals (Appendix G)

Analytes CAS Number MDL1 or

IDL1 (mg/kg)

RL1 (mg/kg)

DQL – USEPA May 2014 Residential RSL

(mg/kg)2,3

Metals by ICP-AES Aluminum 7429-90-5 2.8 10 7700 nc Cobalt 7440-48-4 0.053 5 2.3 nc Iron 7439-89-6 5.23 10 5500 nc

Metals by ICP-MS Arsenic 7440-38-2 0.003 0.10 0.67 c Chromium (total) 7440-47-3 0.00438 0.20 12000 nc Thallium 7440-28-0 0.00239 0.10 0.078 nc Uranium (total) 7440-61-1 see below 23 nc U-235 see total uranium 0.002 0.014 see total uranium U-238 see total uranium 0.0132 0.040 see total uranium Vanadium 7440-62-2 0.0164 0.20 39 nc

Hexavalent Chromium Chromium (hexavalent)

18540-29-9 0.057 0.40 0.3 c

1 Laboratory RLs, MDLs (GEL), and IDLs (ALS) are updated periodically and are dependent on aliquot weight and percent moisture of the samples. MDLs and IDLs are updated periodically; the current MDLs and IDLs at the time of analyses will be used.

2 Nondetects for ICP-AES and ICP-MS analyses will be reported at the MDLs or IDLs to ensure achievement of the DQL.

3 Regional Screening Levels for Chemical Contaminants at Superfund Sites. May 2014. http://www.epa.gov/region09/superfund/prg/index.html. Values for residential soil. If RSL is based on a noncancer endpoint (nc), the RSL is adjusted to a hazard quotient of 0.1 by multiplying the RSL by 0.1. The risk level is 1E-6 if the RSL is based on a cancer endpoint (c).

CAS – Chemical Abstracts Service DQL – Data Quality Level ICP-AES – Inductively Coupled Plasma-Atomic Emission Spectroscopy ICP-MS – Inductively Coupled Plasma-Mass Spectrometry IDL – Instrument Detection Limit MDL – Method Detection Limit mg/kg – milligrams per kilogram RSL – Regional Screening Level RL – Reporting Limit USEPA – United States Environmental Protection Agency

http://www.epa.gov/region09/superfund/prg/index.html

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Date: May 2015


Table A-3b Target Analytes, Reporting Limits, and Data Quality Levels for Metals (Appendix H)

Analytes CAS Number MDL1 or

IDL1 (mg/kg)

RL1 (mg/kg)

DQL – USEPA May 2014 Residential RSL

(mg/kg)2,3

Metals by ICP-AES Arsenic4 7440-38-2 2 4 0.67 c Lead4 7439-92-1 0.7 2 N/A Thallium4 7440-28-0 0.8 2 0.078 nc

Metals by ICP-MS Arsenic 7440-38-2 0.2 0.5 0.67 c Lead 7439-92-1 0.02 0.05 N/A Thallium 7440-28-0 0.002 0.02 0.078 nc

1 Laboratory RLs, MDLs and IDLs are updated periodically and are dependent on aliquot weight and percent moisture of the samples. MDLs and IDLs are updated periodically; the current MDLs and IDLs at the time of analyses will be used.

2 Nondetects for ICP-AES and ICP-MS analyses will be reported at the MDLs or IDLs to ensure achievement of the DQL.

3 Regional Screening Levels for Chemical Contaminants at Superfund Sites. May 2014. http://www.epa.gov/region09/superfund/prg/index.html. Values for residential soil. If RSL is based on a noncancer endpoint (nc), the RSL is adjusted to a hazard quotient of 0.1 by multiplying the RSL by 0.1. The risk level is 1E-6 if the RSL is based on a cancer endpoint (c).

4 This analyte will be initially analyzed by method SW-846 6020; however, the analyte may need to be reanalyzed by SW-846 6010 if the analyte concentration exceeds the calibration range of SW-846 6020. If possible, the associated sample(s) will be reanalyzed by SW-846 6020 at an appropriate dilution to bring the analyte concentration within the SW-846 6020 calibration range; however, if the dilution level is a source of failed QC results, then the associated sample(s) will be reanalyzed via SW-846 6010.

CAS – Chemical Abstracts Service DQL – Data Quality Level ICP-AES – Inductively Coupled Plasma-Atomic Emission Spectroscopy ICP-MS – Inductively Coupled Plasma-Mass Spectrometry IDL – Instrument Detection Limit MDL – Method Detection Limit mg/kg – milligrams per kilogram N/A – not applicable; lead is being analyzed solely for use in evaluating the accuracy of field screening instrumentation

(see Section 13 of Appendix H for further discussion). RSL – Regional Screening Level RL – Reporting Limit USEPA – United States Environmental Protection Agency

http://www.epa.gov/region09/superfund/prg/index.html

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Table A-4 MDC and Data Quality Levels for Primary Radionuclide Target Analytes

Radionuclides1 MDC2 (pCi/g)

DQL – Residential Soil PRG (pCi/g) 3

Potassium-40 0.5 8.36E-02 Cobalt-60 0.1 3.20E-02 Barium-137m 0.1 1.60E+05 Cesium-1374 -4 -4 Thallium-208 0.1 2.05E+04 Lead-210 1.0 1.90E-02 Bismuth-211 -5 2.69E+06 Lead-211 -5 3.95E+01 Bismuth-212 0.5 1.70E+01 Lead-212 0.1 6.44E-01 Bismuth-214 0.1 6.43E+01 Lead-214 0.1 4.73E+01 Radon-219 -5 7.04E+07 Francium-223 -5 2.11E+00 Radium-223 -5 6.65E-02 Thorium-227 -5 3.35E-01 Actinium-228 0.2 8.58E+00 Protactinium-231 -5 8.86E-02 Thorium-231 -5 7.36E+00 Protactinium-234m 4.5 1.03E+07 Thorium-234 4.5 6.95E-01 Uranium-235 0.2 1.07E-01 Americium-2414 -4 -4 1 The radionuclides listed in this table are based on the USEPA approved gamma spectroscopy library

presented in Attachment B. 2 MDCs are based upon sample volume, instrument background, detector efficiency, count time and

other statistical factors, as well as specific isotopic values such as abundance and half-life. 3 USEPA Preliminary Remediation Goals for Radionuclides. Updated November 2014. As the

download tables were not available as of 11/6/2014, the on-line calculator was used to derive PRGs for the residential scenario using all defaults from the calculator. http://epa-prgs.ornl.gov/radionuclides/download.html. DQLs for which Residential Soil PRGs are available for the isotope and its progeny. The DQL represents the lower of the Residential Soil PRGs for the isotope and its progeny.

4 Cs-137 and Am-241 will be reported for each sample, but the results will be used by the laboratory as QC checks on instrument calibration (i.e., efficiency and energy). These radionuclides are not naturally occurring radioactive material (NORM), but are in the environment due to world-wide nuclear activities.

5 The laboratory gamma spectroscopy library includes those isotopes that are used to directly or indirectly quantify the primary target radionuclides listed above. Due to the parent/progeny relationship with the isotopes in the gamma spectroscopy library, MDCs are not established for all isotopes on the library list. MDCs establish the detection limits for the primary radionuclide target analytes.

pCi/g – picoCuries per gram

http://epa-prgs.ornl.gov/radionuclides/download.html

http://epa-prgs.ornl.gov/radionuclides/download.html

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Radionuclides1 MDC2 (pCi/g)

DQL – Residential Soil PRG (pCi/g) 3

DQL – Data Quality Level MDC – Minimum Detectable Concentration NORM – Naturally Occurring Radioactive Material PRG – Preliminary Remediation Goal QC – Quality Control

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Table A-5a Quality Control Performance Criteria for Soil Samples (Appendix G)

Analytes or Radionuclides

Field and Lab Blanks

Field Duplicate %RPD1

LCS % R2

Matrix Spike % R2

Duplicate % RPD2

Metals by 3050/6010C/6020A & 3060/7199 Aluminum <RL 30 47 – 1523 75-125 20 Arsenic <RL 30 82.3 - 1173 75-125 20 Chromium (total) <RL 30 81.8 - 1183 75-125 20 Chromium (hexavalent) <RL 30 80 - 1203 85-115 20 Cobalt <RL 30 83.2 -1163 75-125 20 Iron <RL 30 50.6 -1493 75-125 20 Thallium <RL 30 78.2 -1203 75-125 20 Uranium (total) (calculated from U-235 and U-238) Uranium-235 <RL 30 75-125 75-125 20 Uranium-238 <RL 30 75-125 75-125 20 Vanadium <RL 30 73.5 -1263 75-125 20

Radionuclides by Gamma Spectroscopy Potassium-40 <MDC 30 75-125 NA 20 Cobalt-60 <MDC 30 75-125 NA 20 Barium-137m <MDC 30 75-125 NA 20 Cesium-1374 <MDC 30 75-125 NA 20 Thallium-208 <MDC 30 75-125 NA 20 Lead-210 <MDC 30 75-125 NA 20 Bismuth-211 <MDC 30 75-125 NA 20 Lead-211 <MDC 30 75-125 NA 20 Bismuth-212 <MDC 30 75-125 NA 20 Lead-212 <MDC 30 75-125 NA 20 Bismuth-214 <MDC 30 75-125 NA 20 Lead-214 <MDC 30 75-125 NA 20 Radon-219 <MDC 30 75-125 NA 20 Francium-223 <MDC 30 75-125 NA 20 Radium-223 <MDC 30 75-125 NA 20 Thorium-227 <MDC 30 75-125 NA 20 Actinium-228 <MDC 30 75-125 NA 20 Protactinium-231 <MDC 30 75-125 NA 20 Thorium-231 <MDC 30 75-125 NA 20 Protactinium-234m <MDC 30 75-125 NA 20

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Analytes or Radionuclides

Field and Lab Blanks


LCS % R2

Matrix Spike % R2

Duplicate % RPD2

Thorium-234 <MDC 30 75-125 NA 20 Uranium-235 <MDC 30 75-125 NA 20 Americium-2414 <MDC 30 75-125 NA 20

1 RPD criteria when results are less than 5x RL < 60%. 2 Control limits current at the time of analyses will be used. 3 Represents the limits on the Certificate of Analysis supplied by the vendor or limit supplied by ALS Rochester. 4 Cs-137 and Am-241 will be reported for each sample, but the results will be used by the laboratory as QC checks

on instrument calibration (i.e., efficiency and energy). These radionuclides are not NORM, but are in the environment due to world-wide nuclear activities.

5 The gamma spectroscopy analysis will quantify gamma-emitting radionuclides provided in Table A-4. Many of these radionuclides are decay progeny of parent radionuclides that are Pines Area of Investigation constituents of concern (COCs) and they will be used to directly quantity the activity of the parent COC. Parent COC concentrations are equivalent to or a constant factor of the progeny radionuclides given that the decay chains will be in secular equilibrium following a 28-day buildup time.

LCS – Laboratory Control Sample MDC – Minimum Detectable Concentration (radionuclides only) NA – Not Applicable NORM – Naturally Occurring Radioactive Material QC – Quality Control RL – Reporting Limit % R - Percent Recovery RPD – Relative Percent Difference

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Table A-5b Quality Control Performance Criteria for Soil Samples (Appendix H)

Analytes Field and Lab Blanks


LCS % R2

Matrix Spike % R2

Duplicate % RPD2

Metals by 3050/6010C/6020A

Arsenic <RL 30 82 - 1173

78 - 1224 75-125 20

Lead <RL 30 82-1183

79-1214 75-125 20

Thallium <RL 30 78-1213

79-1204 75-125 20

1 RPD criteria when results are less than 5x RL < 60%. 2 Control limits current at the time of analyses will be used. 3 Represents the limits on the Certificate of Analysis supplied by the vendor or limit supplied by ALS Kelso for Method

6010C. 4 Represents the limits on the Certificate of Analysis supplied by the vendor or limit supplied by ALS Kelso for Method

6020A.

LCS – Laboratory Control Sample RL – Reporting Limit % R - Percent Recovery RPD – Relative Percent Difference

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Table B-1 Summary of Sample Container, Preservation, and Holding Time Requirements for Soil and CCB/Soil Mixture Samples

Parameter Container 1, 2 Preservation Holding Time 3 Metals (Appendix G) Al, As, Co, Cr, Fe, Tl, U (total), and V

Wide-mouth 500-mL glass or plastic jar4

Cool, 0 - 6°C 180 days

Metals (Appendix H) As, Pb, Tl

Wide-mouth 500-mL glass or plastic jar4

Cool, 0 - 6°C 180 days

Hexavalent chromium Wide-mouth 500-mL glass or plastic jar4, 5

Cool, 0 - 6°C 24 hours for ORP, pH, and ferrous iron 30 days to extraction, 7 days from extraction to analysis for hexavalent chromium

Radionuclides6 Wide-mouth 500 mL glass or plastic jar4

None required None required

Particulate matter (PLM, XRD, XRF, LOI)

Wide-mouth 4-oz glass jar4

None required None established

1 Additional volume will be collected for MS/MSD samples (metals only). 2 Laboratory may provide alternate containers as long as the containers meet the requirements of the method and allow

the collection of sufficient volume to perform the analyses. 3 Holding time begins from date and time of sample collection. 4 Glass containers will be placed in zipper-lock bags prior to shipping. 5 In association with the hexavalent chromium analyses, additional parameters will be analyzed. These parameters

either confirm the reducing/oxidizing tendency of the samples or are indirect indicators of the reducing/oxidizing tendency, and include pH, oxidation reduction potential (ORP), Total Organic Carbon (TOC), sulfides, and ferrous iron. To ensure adequate volume, a separate container from other metals will be collected. These results will be used qualitatively.

6 Refer to Table A-4 and Attachment B (gamma spectroscopy library) for the list of radionuclides that will be reported for this program.

mL – milliliter oz – ounce °C – degrees Celsius CCB – Coal Combustion By-product LOI – Loss on Ignition MS/MSD – Matrix Spike/Matrix Spike Duplicate ORP – Oxidation Reduction Potential PLM – Polarized Light Microscopy TOC – Total Organic Carbon XRD – X-Ray Diffraction XRF – X-Ray Fluorescence

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Table B-2 Analytical Methodologies

Analyte Group1 Laboratory SOP Number2 Equivalent Method Number

Metals (Appendix G) Metals by ICP-AES (Al, Co, Fe)

MET-3050B, Rev. 5 MET-200.7/6010C, Rev. 14

USEPA SW-846 Method 3050B USEPA SW-846 Method 6010C

Metals by ICP-MS (As, Cr, Tl, V)

MET-3050B, Rev. 5 MET-6020A/200.8, Rev. 2

USEPA SW-846 Method 3050B USEPA SW-846 Method 6020A

Uranium (Total) (calculated from U-235 and U-238)

GL-MA-E-009, Rev. 22 GL-MA-E-014, Rev. 25


Hexavalent Chromium

GEN-3060, Rev. 3 GEN-7199, Rev. 6

USEPA SW-846 Method 3060A USEPA SW-846 Method 7199

Metals (Appendix H) Metals by ICP-AES (As, Pb, Tl) 3

MET-3050B, Rev. 14 MET-200.7/6010C, Rev. 25

USEPA SW-846 Method 3050B USEPA SW-846 Method 6010C

Metals by ICP-MS (As, Pb, Tl) 3

MET-3050B, Rev. 14 MET-6020A/200.8, Rev. 16


Radionuclides Radionuclides by Gamma Spectroscopy

GL-RAD-A-013, Rev. 25 GL-RAD-A-021, Rev. 20 GL-RAD-I-001, Rev 19

DOE EML HASL 300

Particulate Matter PLM See Section B.4.1.2 Modified, EPA 600/R‐93/116, Test Method for the

Determination of Asbestos in Bulk Building Materials.

XRD See Section B.4.1.2 ASTM D934, Standard Practices for Identification of Crystalline Compounds in Water-Formed Deposits by X-ray Diffraction

XRF See Section B.4.1.2 ASTM D4326, Standard Method for Analysis of Coal and Coal Ash by X-ray Fluorescence

LOI See Section B.4.1.2 ASTM D7348, Standard Test Methods for Loss on Ignition (LOI) of Solid Combustion Residues

1 See Tables A-3 and A-4 and Attachment B (gamma spectroscopy library) for the analytes in each analyte group. 2 The version of the SOP that is current at the time of sample analysis will be utilized. Any modification to the approved SOP will

require USEPA notification and concurrence. 3 If the analyte(s) concentration(s) exceeds the calibration range of SW-846 6020, the associated sample(s) will be analyzed at an

appropriate dilution in order to bring the analyte(s) concentration(s) within the 6020 calibration range; however, if the dilution level is a source of failed QC results then the associated sample(s) will be reanalyzed via SW-846 6010.

DOE – Department of Energy EML – Environmental Measurements Laboratory HASL – Health and Safety Laboratory ICP-AES – Inductively Coupled Plasma-Atomic Emission Spectroscopy ICP-MS – Inductively Coupled Plasma-Mass Spectrometry LOI – Loss on Ignition NA – Not Available

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Analyte Group1 Laboratory SOP Number2 Equivalent Method Number

PLM – Polarized Light Microscopy SOP – Standard Operating Procedure USEPA – United States Environmental Protection Agency XRF – X-ray Fluorescence XRD – X-ray Diffraction

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Table B-3 Analytical Quality Control Checks Parameter/

Method QC Check Frequencies1 Control Limits Laboratory Corrective Actions

Metals 6010C

Reagent/prep/ ICBK blanks

One per preparation batch

No analytes above RL

Repreparation/reanalysis of entire prep batch

MS samples One per preparation

batch One per preparation

batch Analyze post-digestion

spike Duplicate samples


Refer to Table A-5 Check analytical system, flag results

LCS One per preparation batch

Vendor limits (refer to Table A-5)


Dilution test One per preparation batch

Within 10% of original sample

results

Flag results

Interference check

Beginning of each analytical run

20% of true values Recalibrate and reanalyze any sample

with interfering elements

Metals 6020A

Reagent/Prep/ ICBK/CCBK

blanks

1 per analytical batch of 20 samples or less, CCBs every

10 samples in analytical run

No analytes above RL


MS Samples 1 per analytical batch of 20 samples

or less

Refer to Table A-5 Analyze post digestion spike

MS Duplicate Samples

1 per analytical batch of 20 samples

or less


LCS 1 per analytical batch of 20 samples

or less



Dilution Test 1 per analytical batch of 20 samples

or less

10% (results >4 x RL)

Flag results

Interference check

Beginning of each analytical run

80-120% R Recalibrate, reanalyze any sample with

interfering elements

Hexavalent Chromium 7199

Reagent/prep blanks

One per analytical batch of 20 samples

or less

Not detected above MRL

Repreparation/reanalysis of entire batch

MS samples One per analytical batch of 20 samples

or less

Refer to Table A-5 Repreparation/reanalysis of entire batch

Duplicate samples

One per analytical batch of 20 samples

or less


LCS One per analytical batch of 20 samples

or less



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Parameter/ Method QC Check Frequencies1 Control Limits Laboratory Corrective

Actions

Radionuclides Gamma spectroscopy

Reagent/prep blanks


Not detected above MDC


Duplicate samples


RPD <20; RPD<100 if SR <5x MDC; RPD

NA if SR <MDC

Check analytical system, flag results

LCS One per preparation batch

75-125% R Repreparation/reanalysis of entire batch

Particulate Matter

Duplicate samples


RPD <20 or current laboratory limits

Check results, flag results

1 Preparation Batch defined as maximum of 20 field samples of a similar matrix unless otherwise specified. CCB – Coal Combustion By-product CCBK – Continuing Calibration Blank ICBK – Initial Calibration Blank LCS – Laboratory Control Sample MDC – Minimum Detectable Concentration MRL – Method Reporting Limit MS – Matrix Spike NA – Not Applicable %R – Percent Recovery QC – Quality Control RL – Reporting Limit RPD – Relative Percent Difference SR – Sample Result

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Table B-4 Maintenance Procedures and Schedule for Field Instruments Instrument Maintenance Procedures/Schedule Spare Parts in Stock

Portable radiation detection instruments

Physical check of instrument/daily Check the battery and change/recharge if necessary/daily High voltage check/daily Response correlation check/beginning of the program

Batteries Source standard

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Table B-5 Maintenance Procedures and Schedule for Analytical Instruments

Instrument Spare Parts Activity Frequency

ICP-AES (SW-846 Method 6010C)

Gases O-rings Tubing

Check gases Check argon tank pressure Check aspiration tubing Check vacuum pump gauge Check cooling water system Check nebulizer Check capillary tubing Check peristaltic pump tubing Check high voltage switch Check exhaust screens Check torch, glassware, aerosol injector tube, bonnet Clean plasma torch assembly Clean nebulizer and drain chamber Clean filters Replace tubing Check o-rings

Daily Daily Daily Daily Daily Daily Daily Daily Daily Daily Daily Monthly or as needed Monthly or as needed Monthly or as needed Monthly or as needed Monthly or as needed

ICP-MS (SW-846 Method 6020A)

Gases O-rings Tubing

Clean nebulizer tip after use Replace peripump sample introduction tubing Change pump hoses on drain systems Check drain waste collection containers, and empty as necessary Check Neslab water level and add water if required Clean/replace interface cones Clean/replace nebulizer Clean/replace torch Check/replace water filter

As needed As needed As needed As needed As needed As needed As needed As needed As needed

Change oil in interface rotary pump (or as needed). Clean ion lenses 4-6 months (or as needed).

Quarterly Quarterly

Clean air filters 6 months Change pump oil in backing rotary pump Evaluate/replace EM

12 months

Ion Chromatography Method (SW-846 Method 7199)

Rinse IC pump and valves Lubricate pump

Weekly Every 6 months

Gamma Spectrometer (DOE EML HASL 300)

Energy and FWHM calibration Efficiency calibration Instrument check Background Liquid nitrogen fill Software backups Filter cleaning

Annual Annual Daily Weekly Weekly Monthly Quarterly

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Instrument Spare Parts Activity Frequency

DOE – Department of Energy EM – Electron Multiplier EML – Environmental Measurements Laboratory FWHM – Full Width at Half Maximum HASL – Health and Safety Laboratory IC – Ion Chromatograph ICP-AES – Inductively Coupled Plasma-Atomic Emission Spectroscopy ICP-MS – Inductively Coupled Plasma-Mass Spectrometry

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Table B-6 Laboratory Equipment Monitoring Equipment Type Activity Frequency

Ovens Temperature monitoring Electronics serviced

Daily As needed

Refrigerators Temperature monitoring Refrigerant system and electronics serviced

Twice daily As needed

Balances Calibration Manufacturer cleaning and servicing

Daily or before use Annually

High-purity water system Conductance monitoring Daily

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Table B-7 Field Instrument Calibration

Parameter Calibration Frequency Calibration Standards Acceptance Criteria

Gamma Walk-over Survey (Ludlum Model 44-10 detector)

Annually: At least once per year and after repairs have been performed, if applicable.1

NIST Traceable sources

Calibrated by the manufacturer or a rental vendor with detector efficiency optimized for gamma energies associated with Ra-226 and its decay progeny

Daily: Field response check

Exempt sealed gamma source

Within 20% of source activity

Gamma Dose Rate Survey (Thermo Scientific™ Micro Rem r)

Annually: At least once per year and after repairs have been performed, if applicable.

NIST Traceable sources

Calibrated by the manufacturer or a rental vendor

Daily: Field response check

Exempt sealed gamma source

Within 20% of source activity

¹ Note that the detector will be correlated to a source block set (4 stacked blocks) with known total radium concentration; a 10 pCi/g total radium source block set is located at the former Kerr McGee Rare Earths Facility in West Chicago, Illinois.

NIST – National Institute of Standards and Technology pCi/g – picoCuries/gram SSC – Supplemental Soil Characterization

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Table B-8 Analytical Instrument Calibration Instrument and

Method Calibration Frequency

Calibration Standards Acceptance Criteria1

Metals by ICP-AES SW-846 6010C

Initial: Daily Initial: Per manufacturer’s instructions. Minimum of one standard and calibration blank and instrument blank.

Initial: Highest standard within 10% of true value. % RSD 20 < RL

Continuing: Every 10 samples

Mid-level of each metal and instrument blank

±10% of true value % RSD 20 < RL

Ending Mid-level of each metal and instrument blank

±10% of true value % RSD 20 < RL

Metals by ICP-MS SW-846 6020A

Instrument tune: Daily

Per manufacturer: tune solution of 10 ug/L, Be, Mg, Co, In, Pb

Manufacturer’s recommended tune criteria as specified in SOP.

Initial: Daily Initial per manufacturer’s instructions – minimum of one calibration standard, one calibration blank and interference check standards ICS-A, ICS-AB

±10% true value % RSD 20 <RL ±20% recovery

Continuing: every 10 samples

One calibration standard and one calibration blank

±10% true value % RSD 20 <RL

Ending If required: run MRL standard , ICS-A and ICS-AB interference check standards, one calibration standard, one calibration blank

±20% recovery ±10% true value % RSD 20 <RL

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Instrument and Method

Calibration Frequency

Calibration Standards Acceptance Criteria1

Hexavalent chromium by SW-846 7199

Initial: Daily 3 standards plus blank r ≥ 0.999 ±10% of true value < RL

Continuing: Every 10 injections, or 24 hours, whichever is more frequent

Mid-level plus blank ±10% of true value < RL

Ending Mid-level plus blank ±10% of true value < RL

Radionuclides by Gamma Spectroscopy (DOE EML HASL 300)

Daily checks using a check source with multiple radionuclides

NIST Traceable standards

Within 2-3 sigma control limits

Monitor FWHM and efficiency

NIST Traceable standards

Within 2-3 sigma control limits

Peak centroid NIST Traceable standards

+/- 2 keV

Weekly or monthly background checks

NA Within 2-3 sigma control limits

1 If criteria are not met, corrective actions as specified in the laboratory SOPs (Attachment A) are taken. DOE – Department of Energy EML – Environmental Measurements Laboratory FWHM – Full Width at Half Maximum HASL – Health and Safety Laboratory ICP-AES – Inductively Coupled Plasma-Atomic Emission Spectroscopy ICP-MS – Inductively Coupled Plasma-Mass Spectrometry ICS – Interference Check Sample KeV – kiloelectron volt MRL – Method Reporting Limit NA – Not Applicable NIST – National Institute of Standards and Technology RL – Reporting Limit RSD – Relative Standard Deviation SOP – Standard Operating Procedure ug/L – micrograms per Liter

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Section: Figure Revision: 2

Date: November 2014 Page: 1 of 1


Figure

Figure A-1 Project Organization Chart

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Section: Attachment A Revision: 3

Date: May 2015


Attachment A Laboratory Standard Operating Procedures

A-1 ALS Rochester

A-2 GEL

A-3 ALS Kelso

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Section: Attachment B Revision: 3

Date: May 2015


Attachment B Gamma Spectroscopy Library

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Section: Attachment C Revision: 3

Date: May 2015


Attachment C Radioisotope Calculation Spreadsheet

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Section: Attachment A Revision: 3

Date: May 2015

Attachment A Laboratory Standard Operating Procedures

A-1 ALS Rochester

A-2 GEL

A-3 ALS Kelso


ALS Standard Operating Procedure

DOCUMENT TITLE: DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA-MASS

SPECTROSCOPY (ICP-MS) REFERENCED METHOD: EPA 200.8, SW 6020A

SOP ID: MET-6020A/200.8 REV. NUMBER: 2

EFFECTIVE DATE: 11/4/2013

If this SOP is accessed electronically outside of the ALS Rochester Intranet website, it is an uncontrolled-copy and will not be updated.

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Metals by ICP-MS MET-6020A/200.8, Rev 2 Effective: 11/4/2013 Page i of i

R I G H T S O L U T I O N S | R I G H T P A R T N E R

STANDARD OPERATING PROCEDURE

TABLE OF CONTENTS 1) Scope and Applicability .............................................................................................................. 1 2) Summary of Procedure ............................................................................................................... 1 3) Definitions ................................................................................................................................. 2 4) Health and Safety Warnings........................................................................................................ 3 5) Cautions .................................................................................................................................... 4 6) Interferences.............................................................................................................................. 5 7) Personnel Qualifications and Responsibilities ............................................................................. 5 8) Sample Collection, Containers, Preservation, and Storage ........................................................... 6 9) Equipment and Supplies............................................................................................................. 6 10) Standards and Reagents............................................................................................................. 7 11) Method Calibration .................................................................................................................... 8 12) Sample Preparation and Analysis .............................................................................................. 10 13) Troubleshooting –.................................................................................................................... 10 14) Data Acquisition ...................................................................................................................... 11 15) Calculations and Data Reduction Requirements ........................................................................ 11 16) Quality Control, Acceptance Criteria, and Corrective Action ...................................................... 13 17) Data Records Management....................................................................................................... 15 18) Contingencies for Handling Out-Of-Control Data ...................................................................... 15 19) Method Performance ................................................................................................................ 15 20) Summary of Changes ............................................................................................................... 16 21) References and Related Documents.......................................................................................... 16 22) Appendix ................................................................................................................................. 16


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DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA-MASS SPECTROSCOPY (ICP-MS)

1) Scope and Applicability

This SOP uses EPA SW846 Method 6020A for the determination of the concentrations of certain elements in water, soil, aqueous and non-aqueous wastes, and sediment samples. This SOP also uses EPA 200.8 for the determination of the concentrations of certain elements in drinking water, ground water, and surface water. The scope of this document does not allow for the in-depth descriptions of the relevant spectroscopic principles required for gaining a complete level of competence in this scientific discipline.

The analytes and reporting limits are listed in Table 1.

2) Summary of Procedure

2.1 Prior to analysis, samples must be digested using appropriate sample preparation methods unless otherwise specified by the client. The preparation for soils is described in MET-3050 and the preparation for waters is described in MET-CLP-DIG. The digestate is analyzed for the elements of interest using ICP spectrometry.

2.2 This method is for the multi-elemental determination of analytes by ICP-MS. The method measures ions produced by a radio-frequency inductively coupled plasma. Analyte species originating in a liquid are nebulized and the resulting aerosol transported by argon gas into the plasma torch. The ions produced are entrained in the plasma gas and introduced, by means of an interface, into a mass spectrometer. The ions produced in the plasma are sorted according to their mass-to-charge ratios and quantified with a channel electron multiplier. Interferences must be assessed and valid corrections applied or the data flagged to indicate problems. Interference correction must include compensation for background ions contributed by the plasma gas, reagents, and constituents of the sample matrix.

2.3 Method Modifications

2.3.1 The concentration of interfering elements in the ICSA and ICSAB solutions are spiked at levels recommended by the manufacturer due to instrument sensitivity.

2.3.2 6020A says that IDLs should be determined every 3 months to monitor noise and response changes. Blanks and MRL standards are analyzed with every run and can be used for monitoring.


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3) Definitions

3.1 Initial Calibration - analysis of analytical standards for a series of different specified concentrations; used to define the linearity and dynamic range of the response of the detector to the element.

3.2 Calibration Standard (CAL) - A solution prepared from the dilution of stock standard solutions. The CAL solutions are used to calibrate the instrument response with respect to analyte concentration.

3.3 Dissolved Analyte - The concentration of analyte in an aqueous sample that will pass through a 0.45 μm membrane filter assembly prior to sample acidification.

3.4 Initial Calibration Verification (ICV) (also called Second Source Calibration Verification) – ICV solutions are made from a stock solution which is different from the stock used to prepare calibration standards and is used to verify the validity of the initial calibration.

3.5 Continuing Calibration Verification Standard (CCV) - A standard analyzed at specified intervals and used to verify the ongoing validity of the instrument calibration. For the LLCCV, see MRL Standard below.

3.6 Matrix Spike (MS) – An aliquot of an environmental sample to which known quantities of all of the elements of client interest are added to a sample matrix prior to sample digestion and analysis. The purpose of the matrix spike is to evaluate the effects of the sample matrix on the methods used for the analyses. Percent recoveries are calculated for each of the analytes detected.

3.7 Duplicate (DUP) - A laboratory duplicate. Two aliquots of the same sample taken in the laboratory and analyzed separately with identical procedures. Analysis of duplicates indicates precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.

3.8 Laboratory Control Sample (LCS) - A matrix blank spiked with all of the elements of client interest. The LCS is analyzed exactly like a sample, and its purpose is to determine whether the methodology is in control and whether the laboratory is capable of making accurate measurements. LCS-Soil is purchased from a vendor.

3.9 Method Blank (MB) - The MB is an artificial sample designed to monitor introduction of artifacts into the process. The method blank is carried through the entire preparation and analytical procedure.

3.10 Instrument Blank (ICB/CCB) - The instrument blank (also called initial or continuing calibration blank) is a volume of reagent water acidified with the same acid matrix as in the calibration standards. This blank is the zero standard and has a reagent composition identical to the digestates. The purpose of the ICB/CCB is to determine the levels of contamination associated with the instrumental analysis.

3.11 Batch – A group of no more than 20 samples analyzed together on the same day with the same reagents. See the SOP for Batches and Sequences (ADM-BATCH) for more detail.

3.12 Calibration Blank – A volume of reagent water acidified with the same acid matrix as in the calibration standards. The calibration blank is a zero standard and is used to the calibrate the instrument.


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3.13 Internal Standard - Pure analyte(s) added to a sample, extract, or standard solution in known amount(s) and used to measure the relative responses of other method analytes that are components of the same sample or solution. The internal standard must be an analyte that is not a sample component.

3.14 Linear Range - The concentration range over which the instrument response to an analyte is linear.

3.15 Limit of Detection (LOD) – An estimate of the minimum amount of a substance that an analytical process can reliably detect. An LOD is analyte- and matrix-specific and may be laboratory – dependent. For DOD, the smallest amount or concentration of a substance that must be present in a sample in order to be detected at a high level of confidence (99%). At the LOD, the false negative rate (Type II error) is 1%.

3.16 Limit of Quantitation (LOQ) – The minimum levels, concentrations, or quantities of a target that can be reported with a specified degree of confidence. For DOD, the lowest concentration that produces a quantitative result within specified limits of precision and bias. The LOQ shall be set at or above the concentration of the lowest initial calibration standard.

3.17 Interference Check Solution (ICS) - A solution of selected method analytes of higher concentrations which is used to evaluate the procedural routine for correcting known interelement spectral interferences with respect to a defined set of method criteria. This is used for 6020A.

3.18 MRL Standard – Standard prepared with a known concentration of elements to check accuracy at the quantitation limit. This is also known as Low-level calibration check standard (LLCCV or LLICV). This standard is not digested.

3.19 LOQ Standard – also called LLQC – Standard prepared at the LOQ that undergoes digestion and preparation procedures.

3.20 HLCCV2 – A standard prepared slightly higher than the calibration range for metals. This is an “upper range limit” standard used to verify the upper limit of the linear dynamic range of the instrument.

3.21 Tune – The analysis of a standard element to verify that the mass spectrometer meets standard mass spectra abundance criteria prior to sample analysis.

3.22 Matrix – the predominant material, component, or substrate (e.g., surface water, soil, etc.) of which the sample to be analyzed is composed.

4) Health and Safety Warnings

4.1 All appropriate safety precautions for handling reagents and samples must be taken when performing this procedure. This includes the use of personal protective equipment, such as safety glasses, lab coat and the correct gloves.

4.2 Chemicals, reagents and standards must be handled as described in the Company safety policies, approved methods and in MSDSs where available. Refer to the Environmental, Health and Safety Manual and the appropriate MSDS prior to beginning this method.

4.3 Hydrochloric and Nitric Acid are used in this method. These acids are extremely corrosive and care must be taken while handling them. A face shield should be used while pouring acids and safety glasses should be worn while working with the solutions. Lab coat and gloves should always be worn while working with these solutions.


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4.4 The use of pressurized gases is required for this procedure. Care should be taken when moving cylinders. All gas cylinders must be secured to a wall or an immovable counter with a chain or a cylinder clamp at all times. Sources of flammable gases (e.g., pressurized hydrogen) should be clearly labeled.

4.5 High Voltage - The RF generator supplies up to 2000 watts to maintain an ICP. The power is transferred through the load coil located in the torch box. Contact with the load coil while generator is in operation will likely result in death. When performing maintenance on the RF generator, appropriate grounding of all HV capacitors must be performed as per manufacturer.

4.6 UV Light - The plasma is an intense source of UV emission, and must not be viewed with the naked eye. Protective lenses are in place on the instrument. Glasses with special protective lenses are available when direct viewing of the plasma is necessary.

4.7 Refer to the Safety Manual for further discussion of general safety procedures and information.

4.8 Waste Management and Pollution Prevention

It is the laboratory’s practice to minimize the amount of acids and reagent used to perform this method wherever feasible. Standards are prepared in volumes consistent with methodology and only the amount needed for routine laboratory use is kept on site. The threat to the environment from solvent and reagents used in this method can be minimized when disposed of properly.

The laboratory will comply with all Federal, State and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions as specified in the EH&S Manual.

Samples with analyte concentrations exceeding TCLP regulatory limits are disposed of as hazardous waste, see the SOP for Sample Disposal (SMO-SPLDIS).

5) Cautions

Preventive maintenance activities listed below should be performed when needed as determined by instrument performance (i.e. stability, sensitivity, etc.) or by visual inspection. Other maintenance or repairs may, or may not require factory service, depending on the nature of the task.

• cone removal and cleaning

• removal and cleaning of ICP glassware and fittings

• checking air filters and cleaning if necessary

• checking the rotary pump oil and adding or changing if necessary

• removal and cleaning of extraction lens

• removal and cleaning of ion lens stack


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6) Interferences

6.1 Isobaric elemental interferences in ICP-MS are caused by isotopes of different elements forming atomic ions with the same nominal mass-to-charge ratio (m/z). A data system must be used to correct for these interferences. This involves determining the signal for another isotope of the interfering element and subtracting the appropriate signal from the analyte isotope signal. Attention should be given to circumstances where very high ion currents at adjacent masses may contribute to ion signals at the mass of interest. Matrices exhibiting a significant problem of this type may require resolution improvement, matrix separation, or analysis using another isotope.

6.2 Isobaric molecular and doubly-charged ion interferences in ICP-MS are caused by ions consisting of more than one atom or charge, respectively. Most isobaric interferences that could affect ICP-MS determinations have been identified in the literature. Refer to Method 6020A for further discussion.

6.3 Physical interferences are associated with the sample nebulization and transport processes as well as with ion-transmission efficiencies. Nebulization and transport processes can be affected if a matrix component causes a change in surface tension or viscosity. Changes in matrix composition can cause significant signal suppression or enhancement. Total solid levels below 2000 mg/L have been recommended to minimize solid deposition on the nebulizer tip. An internal standard can be used to correct for physical interferences, if it is carefully matched to the analyte so that the two elements are similarly affected by matrix changes.

6.4 Memory interferences can occur when there are large concentration differences between samples or standards which are analyzed sequentially. The rinse period between samples must be long enough to eliminate these interferences.

7) Personnel Qualifications and Responsibilities

7.1 It is the responsibility of the analyst to perform the analysis according to this SOP and to complete all documentation required for data review. Analysis and interpretation of the results are performed by personnel in the laboratory who have demonstrated the ability to generate acceptable results utilizing this SOP. This demonstration is in accordance with the training program of the laboratory. Final review and sign-off of the data is performed by the department supervisor/manager or designee.

7.2 Training – see CE-QA003.


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8) Sample Collection, Containers, Preservation, and Storage

8.1 Solid samples require no preservation prior to analysis other than storage at 0-6°C. Sample containers may be glass or plastic. When the laboratory provides the sample containers, the containers are glass soil jars with Teflon-lined lids.

8.2 For aqueous samples, glass or plastic sample containers are acceptable. When the laboratory provides the sample containers, the containers are certified clean 500 mL plastic bottles. Sample volume should be acid preserved with (1+1) nitric acid to pH <2. Samples are held at room temperature (although refrigeration is acceptable also).

8.3 For the determination of the dissolved elements, the sample must be filtered through a 0.45 μm pore diameter membrane filter at the time of collection or as soon thereafter as practically possible. (Glass or plastic filtering apparatus are recommended to avoid possible contamination. Only plastic apparatus should be used when the determinations of boron and silica are critical.) Samples should be filtered prior to acidification, because acidification changes the sample (usually by dissolving particulates that would be filtered out). Acidified samples received at the lab that require lab filtration must be noted in the case narrative. See digestion SOPs for filtration procedure.

8.4 Samples are generally received in the ICP-MS laboratory as 1% Nitric Acid digestates. Digestates are stored at room temperature in hotblock cups or B-cups. There is no specific holding time from digestion to analysis. Client samples must be analyzed within 6 months of collection.

8.5 Following analysis, digestates are stored until all results have been reviewed. Digestates are diluted and disposed of through the sewer system in approximately 90 days after receipt of sample.

8.6 For more information about custody, sample handling, and storage procedures, see SMO-GEN and SMO-ICOC.

9) Equipment and Supplies

Instrument ID Instrument Configuration Manufacturer Part Serial Number Year

Acquired

SCIEX ICP/MS Perkin Elmer Elan 9000 PO370203

Autosampler PE AS93Plus

Computer Workstation Dell Optiplex GX150

ICPMS (R-ICP-MS-01)

Analytical Software ELAN v.2.4

2002

The system has a mass range from at least 6 to 240 amu and a data system which allows corrections for isobaric interferences and the application of the internal standard technique.

9.1 Peristaltic Pump and pump tubing

9.2 15 and 50 mL autosampler tubes

9.3 Pipettes (Eppendorf) – calibrated according to ADM-PCAL.

9.4 Volumetric flasks, class A


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10) Standards and Reagents

10.1 Standards Preparation General Information and Disclaimers

All of the preparation instructions are general guidelines. Other technical recipes may be used to achieve the same results. Example – a 20 mg/L standard may be made by adding 1 mL of 200 mg/L to 10 mLs or may be made by adding 4 mL of 50 mg/L to 10 mL. The preparation depends upon the final volume needed and the initial concentration of the stock. Reasonable dilution technique is used.

Vendors and vendors’ products are sometimes listed for the ease of the analyst using this SOP, but products and purchased concentrations are examples only and subject to change at any time. All purchased standards are certified by the vendor. Certificates of Analysis are kept in the department until the standards are no longer being used – at which time they are filed with QA. Certificates of Analysis are available upon request. Purchased standards are routinely checked against an independent source for both analyte identification and analyte concentration.

All Standards must be traceable using the laboratory lot system (CE-QA007).

All preparatory information for the standards and QC samples are provided in the Controlled Forms section of the Rochester Intranet in the Metals Standards Logbooks. They are all stored in plastic at room temperature.

10.2 Argon – 99.99% purity

10.3 Trace metals grade chemicals shall be used in all tests. Each lot of acid used is to be analyzed to demonstrate that it is free of interference before use (CE-GEN007). All acids are stored at room temperature. Acids expire per the recommendations in Expiration Policy (CE-QA012) if no other indication is given.

• Hydrochloric acid (conc.), HCl. Purchased commercially

• Nitric acid (conc.), HNO3. Purchased commercially.

10.4 Reagent Water. All references to water in this SOP refer to the water produced by the laboratory water system.

10.5 Standards

10.5.1 Mixed Calibration Standards are prepared by combining appropriate volumes of the stock solutions in volumetric flasks. Matrix match with the appropriate acid and dilute to 500 mL with water. Calibration standards should be verified using a second source quality control sample (LCS or ICV). Calibration standards expire in 1 month.

10.5.2 Initial Calibration Verification (ICV) Standard is prepared by combining compatible analytes at concentrations equivalent to the midpoint of their respective calibration curves. The ICV standard should be prepared from a separate source independent from that used in the calibration standards. ICV standard expires in 48 hours.

10.5.3 Continuing Calibration Verification (CCV) Standard is prepared by combining compatible analytes at concentrations equivalent to the midpoint of their respective calibration curves. The CCV standard is prepared from a separate source as that used in the calibration standards. CCV standard expires in 48 hours.

10.5.4 MRL Standard is prepared to contain known concentrations of elements at the MRL. MRL standard expires in 1 month.


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10.5.5 Interference Check Solutions A and AB are prepared to contain known concentrations of interfering analytes that will provide an adequate test of the correction factors. Used for 6020A only. ICSA / ICSAB standards expire in 1 week.

10.5.6 The spiking solutions for the Laboratory Control Sample and Matrix Spike are purchased as custom mixes at the concentrations recommended in the method. Solutions expire per manufacturer recommended expiration date. The LCS and MS are spiked at digestion according to the preparation SOP. All target analytes are spiked in the LCS and MS.

10.5.7 Internal Standards Solutions-high purity grade solutions are purchased and diluted to final concentration of 1000-5000 ppb. Diluted solutions expire in 6 months.

10.6 Blanks

10.6.1 Method Blanks must contain all the reagents and in the same volumes as used in the preparation of samples. The method blanks are blank matrix samples carried through the complete procedure and contain the same acid concentration in the final solution as the samples.

10.6.2 The Calibration Blank is prepared by acidifying reagent water to the same concentrations of acid found in the standards and samples.

11) Method Calibration

11.1 Refer to method 6020A (Section 11.0) and the instrument manuals for detailed instruction on implementation of the following procedures preceding an analytical run. All of the following are done daily prior to initial calibration unless otherwise specified.

11.2 Initiate plasma and allow a warm up of at least 30 minutes. The tuning procedures may be carried out during warm-up.

11.3 Open the EPA Tune Method

11.3.1 Aspirate 10 ppb tuning solution

11.3.2 Click on Tune Mass Spec button in Tuning Window

11.3.3 Check mass calibration. Measured mass must be within 0.05 amu of actual mass. The resolution must be <0.9 amu full width at 10% peak height. Save and print tune. Put one copy of the tune with the analytical run and another copy in the tune binder.

11.4 Open EPA Daily Method

11.4.1 Aspirate the 10 ppb tuning solution

11.4.2 Click on the Analyze button to acquire

11.4.3 Check that the RSDs for the five replicates are less than 5%

11.4.4 Monitor daily performance measures as recommended by Perkin Elmer for Rh sensitivity, background, % double charged, and % oxide levels.

• Rh>150000 cps for 10 ppb

• Background @ mass 220<30cps (once initial operating conditions have changed, i.e. voltage on detector, RF power, etc, background should be <100 cps. Ensure that desired signal to noise ratio is achieved.)


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• % double charged <4%

• % oxides <4%

Oxides and double charged levels can be reduced by slightly decreasing the nebulizer flow rate.

11.4.5 If the tune and Daily Performance checks do not meet criteria, retune the instrument and reanalyze tuning solution. The tune and Daily must pass before proceeding.

11.5 Open the EPA Lens Calibration method and perform the autolens calibration using 10 ppb tuning solution. This is done as needed.

11.5.1 Clear old calibration

11.5.2 Get analytes

11.5.3 Optimize (Takes about 6 minutes)

11.5.4 Save file

11.6 Open the Neblens power oxides workspace and optimize the following parameter using the 10 ppb tuning solution containing Be, Mg, Co, Rh, In, Ba, Ce, Pb

11.6.1 Set RF power to desired level

• 1500 watts

11.6.2 Optimize the nebulizer argon flow – done as needed

11.6.3 Optimize the static lens voltage – done as needed

11.6.4 Save the optimization file

11.7 Open the EPA 6020 Dual Detector calibration method and aspirate a solution twice the calibration range. All elements plus internal standard elements should be present.

Note: This procedure is required when detector voltages or a new detector is installed. The laboratory does periodically.

11.7.1 Clear old calibration

11.7.2 Get analytes

11.7.3 Optimize (Takes about 20 minutes)

11.7.4 Save file

11.8 Initial Calibration – follow ADM-ICAL. If these instructions conflict with ADM-ICAL, follow the instructions in this SOP.

11.8.1 Number of Calibration standards – 3 standards and a calibration blank are analyzed daily before samples or QC. The correlation coefficient must be greater than 0.998 for each analyte. If the correlation is less than 0.998, recalibrate the instrument prior to analyzing any samples.

11.8.2 The use of internal standards, ICAL calculation, and sample calculation is in the Calculation Section.


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12) Sample Preparation and Analysis

12.1 Digest samples with the appropriate digestion method. For waters, use MET-CLPDIG. For soils, use MET-3050. Digestates originating from soil samples are diluted prior to instrumental analysis to avoid interferences and allow the analysis to achieve maximum sensitivity which results in optimum Reporting Limits.

12.2 Analytical Run

12.2.1 For soil digestates - Dilute 1 mL of digestate to 5 mL with matrix matched reagent water prior to internal standard addition and analysis.

12.2.2 Each 5 mL aliquot of blanks, standards, samples, and sample dilutions are spiked with 50 uL of internal standard solution prior to analysis. Load samples on the autosampler according to the analytical sequence.

12.2.3 Open desired method. Enter sample information. Enter pump control speeds for all samples and save sample file. Re-open the sample file (this must be done for batch QC to run properly) and highlight the row numbers to be analyzed. Select “analyze batch.”

12.2.4 Calibration is done daily using 3 standards and a blank for each analyte. Analyze QC as per the frequency described in the QC Section. See ADM-BATCH for further detail.

12.3 Sample Analysis and Evaluation

12.3.1 Sensitivity, LOD, LOQ, precision, linear dynamic range, and interference effects must be established for each individual analyte line on each particular instrument. All measurements must be within the instrument linear range where the correction equations are valid.

12.3.2 Dilute and reanalyze samples which are above the linear range of the instrument or measure an alternate, less-abundant isotope (if calibrated). See ADM-DIL for more instruction on preparing and documenting sample dilutions.

12.3.3 Evaluate QC according to the QC Section. Repeat samples associated with non-compliant QC whenever possible.

12.3.4 If sample concentration for Ag is greater than 100 ug/L, sample should be redigested at a dilution until the sample solution contains less than 100 ug/L.

13) Troubleshooting –

Maintenance log - All Preventive maintenance, as well as instrument repair, should be documented in the appropriate instrument maintenance log. Most routine maintenance and troubleshooting are performed by ALS staff. The laboratory maintains a service contract with the instrument manufacturer that allows for an unlimited number of service calls and full reimbursement of all parts and labor. Any maintenance performed by outside services must also be documented – either through notes in the log or through documents provided by the service. The log entries will include the date maintenance was performed, symptoms of the problem, serial numbers of major equipment upgrades or replacements. The data file name of the first acceptable run after maintenance is to be documented in the maintenance log.

See instrument manual or maintenance log for help in solving specific analytical or instrument problems.


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14) Data Acquisition

Data is electronically transferred from the instrument software to LIMS. The preparation information entered to LIMS is used by LIMS to calculate the final results – see Calculation Section.

15) Calculations and Data Reduction Requirements

15.1 Calculate sample results using the data system printouts and digestion information. The digestion and dilution information is entered into the data system. The data system then uses the calculations below to generate a sample result.

15.2 Aqueous samples are reported in μg/L:

μg / L (Sample) = C x Dilution Factor x FinalDigestateVolume mlInitialVolumeDigested ml

* ( )( )

C*= Concentration of analyte as measured at the instrument in ug/L (in digestate).

15.3 Solid samples are reported in ug/Kg:

1Kg1000g x

1000ml1L x

(g) wt.Sample(ml) Vol.Digestion

xFactorDilutionDigestion Post x C =(Sample)ug/Kg *


15.4 Internal standards are identified by a caret and are bracketed by elements with which

they are associated.

15.5 Table 2 has the recommended Isotopes. The actual mass used is on the Quantitation report.

15.6 ELAN software assumes that all elements within a standard group are similarly affected by instrument drift or matrix interferences. Changes in measured intensity of the Internal standard are used to create the ratios for correcting measured intensities of an element. A blank (called “Blank Intensity” on quantitation report) is analyzed prior to the ICAL to establish Internal standard intensities. A ratio is calculated from the measured intensity of the sample and the blank intensity for a given Internal standard. This ratio is applied to the measured intensity of the target element and adjusts the measured intensity based on performance of the sample matrix. The adjusted intensity is used to plot the ICAL. Sample concentrations are calculated from adjusted intensities.

15.7 EIS

B III =Intensity Adjusted ∗

Where: IB = Intensity of Internal Standard in Blank Solution

IIS = Intensity of Internal Standard in Measured Solution

IE = Intensity of Element in Measured Solution


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15.8 The adjusted intensity of the standards is plotted against concentration using the

linear regression equation of a line and forced through zero intensity and zero concentration. This calibration curve is assuming that the relationship between concentration (the X values) and intensity (the Y values) is linear and that the following equation describes this relationship:

Y=MX

Where:

X=concentration

Y= adjusted intensity

M=slope of the calibration curve

The intercept is forced to be zero.

Given 2 or more data points, the values for M are calculated using the following equation.

( )

( )∑

∑=

=

12

1

= i

ni

ii

i

n

X

YXM

Where: n=number of standards (includes the blank)

In this equation, the blank is subtracted from all solutions and included in the calculation of the calibration curve

15.9 To avoid bias at the low end of the curve, the curve is forced through zero. Forcing the curve through zero may favor the low end of the curve therefore a MRL standard and high level CCV (HLCCV2) are analyzed to verify both ends of the curve.

15.10 Common isobaric interferences are corrected using equations equivalent to those listed in EPA Methods 6020A and 200.8. Monitoring of multiple isotopes for a single element provides a mechanism for identifying isobaric interferences. If an element has more than one monitored isotope, examination of the concentration calculated for each isotope will provide useful information in detecting a possible spectral interference. Consideration should therefore be given to both primary and secondary isotopes in the evaluation of the sample concentration. In some cases, secondary isotopes may be less sensitive or more prone to interferences than the primary recommended isotopes, therefore differences between the results do not necessarily indicate a problem with data calculated for the primary isotopes. Refer to the Interferences section of EPA Method 6020A and 200.8 for additional descriptions of possible interferences and the mechanisms required for adequately compensating for


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their effects.

15.11 The ArCl correction equation adds artificial signal to the As result when selenium is high. Check to see if there is ArCl interference on As by comparing 52Cr and 53Cr (ClO interferes on 53Cr). If they look about the same, turn the correction equation off and reprocess the data. The data is valid if the QC passed before the equation was turned off. If there is Cl interference, qualify the As result as estimated or report it by ICP.

15.12 Data is reviewed according to ADM-DREV.

16) Quality Control, Acceptance Criteria, and Corrective Action

16.1 Initial Calibration Verification Standard – midlevel (ICV) Analyzed immediately after the calibration using a second source standard to verify the standards in the calibration curve. The results for each analyte must agree within 10% of the expected value. If not, the analyses should be terminated and instrument recalibrated. Investigate the sources and preparation procedures of the standards.

16.2 Continuing Calibration Verification Standard – midlevel (CCV) Analyzed after every 10 samples and at the end of the analytical sequence. The results of the CCV must agree within ±10% of the expected value. If the control limits are exceeded, correct the problem and reanalyze the CCV. If that fails, recalibrate the instrument. Repeat samples bound by the out of control CCV unless the CCV is high and the sample concentration is less than the reporting limit.

16.3 Initial and Continuing Calibration Blank (ICB/CCB) The ICB is analyzed at the beginning of the run. The CCB is analyzed after every 10 samples (immediately following the CCV) and at the end of the run. The CCB must be less than the reporting limit (less than the LOD for DOD). If the control limits are exceeded, correct the problem and reanalyze the CCB. If that fails, recalibrate the instrument. Repeat any samples bound by the out of control CCB. If CCB results are exceeded, these associated data shall be flagged unless the sample concentration is less than the reporting limit.

16.4 MRL Standard (MRL) - A standard at or near the MRL is analyzed at the beginning and end of each analytical run but not before the ICV. If the MRL is at the MRL, the limit is 70-130% of the true value for 6020A. (DOD requires a limit of +/- 20%). If the MRL standard is near the MRL, the limit is 80-120%. If the limits are not met the analysis is stopped and the instrument is recalibrated.

16.5 LOQV (LLQC) – This digested standard spiked at the reporting limit must be analyzed quarterly for DOD (6020A requires “as needed”). The limits are 70-130% for 6020A and LCS limits for DOD. If this QC does not meet these limits, determine the source of the problem. Achieve an acceptable LOQV before continuing.

16.6 HLCCV – analyzed once per daily run. The limit is +/- 10%. If it is out of control, client data above the high ICAL standard should be re-analyzed.

16.7 DUP –

16.7.1 Frequency for 200.8 – 1/10 or one per batch, whichever is greater.

16.7.2 Frequency for 6020A – 1/20 or per batch, whichever is greater.

16.7.3 Limits - The control limits are listed in the Data Quality Objectives Table. Client specific QC recoveries may supercede the limits listed in the QA manual.

16.7.4 Corrective Action - If the control limits are exceeded, the data will be reported with a qualifier.


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16.8 MS –

16.8.1 Frequency for 200.8 - 1/10 or one per batch, whichever is greater

16.8.2 Frequency for 6020A - 1/20 or per batch, whichever is greater

16.8.3 Limits - The control limits are listed in the Data Quality Objectives Table. These limits are 75-125% for 6020A and 70-130% for 200.8. Client specific QC recoveries may supercede the limits listed in the QA manual.

16.8.4 Corrective Action - If the control limits are exceeded, analyze a post-digestion spike. DOD requires project-specific DQOs be examined or contact the client for additional measures. See Table F-8.

16.9 LCS is prepared at a frequency of one per preparation batch, not to exceed 20 samples. The % recovery must be within the limits in the Data Quality Objectives Table. These limits are 80-120% for 6020A waters, 85-115% for 200.8, and per the Manufacturer’s Certificate of Analysis for soils. Client specific QC recoveries may supercede these limits. If the control limits are exceeded, the associated batch of samples will be redigested and reanalyzed for the out of control elements or the data is to be flagged. Exception – if the LCS recovery fails high, elements which are less than the reporting limit may be reported.

16.10 Linear Range Study – performed every 6 months. A high level check standard (HLCCV2) must be within 5% of the expected value. If it is not, repeat the linear range study or reduce the linear range and analyze a new high level check standard.

16.11 Ongoing verification of the detection and quantitation limits is required. See CE-QA011 for requirements.

16.12 Method Blank (MB) Method Blanks must be prepared with each batch of 20 or fewer samples of the same matrix. MB values must not exceed the LOQ (1/2 LOQ for DOD). Fresh aliquots of the samples must be prepared and analyzed again for affected analytes after the source of the contamination has been corrected and acceptable MB values have been obtained. If detections are greater than the limit, the batch needs to be redigested if sample concentration is less than 10 times the concentration found in the method blank. If the sample concentration is less than the reporting limit the sample does not require redigestion.

16.13 Internal standards–

16.13.1 Limits – Evaluate the intensity of each internal standard in each standard and QC compared to the intensity of the internal standards in the initial calibration.

• 200.8: 60-125%

• 6020A: > 70%

16.13.2 Corrective Action - If these limits are not met in the samples, verify that the instrument is not drifting by evaluating the internal standards in the CCBs and dilute the sample five fold and reanalyze with the proper addition of internal standards. Repeat this procedure until the internal standard intensities fall within the limits. If the internal standards are not acceptable for the QC, terminate the analysis, correct the problem, recalibrate, and reanalyze any associated samples.


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16.14 Dilution Test (serial dilution) – One dilution test must be performed for each prep batch of 20 or fewer samples. To perform the Dilution Test, choose a sample which has a concentration within the linear range of the instrument and dilute it 1/5. The result of the dilution must agree within 10% of the original sample determination when concentrations exceed 50X LOQ. If it does not, an interference effect must be suspected and should be noted in the case narrative. (DOD requires post-digestion spike addition if the dilution test fails.)

16.15 Post digestion spike – Perform when the MS fails or, for DOD, if no samples had concentration >50xLOQ. (For DOD, Perform when dilution test fails or analyte concentration for all samples <50 times LOQ) The spike addition should produce a concentration of 10-100 times the LOQ. The Post Digestion Spike recovery should be 75-125% of the true value. If it is not the sample must be diluted and reanalyzed to compensate for the matrix effect. Results must agree within 10% of the original determination. The use of standard-addition may also be used to compensate for this effect, or samples may be flagged.

16.16 Interference Check Standard (ICS) – not required for 200.8

16.16.1 Frequency - Solutions A and AB are analyzed at the beginning of each analytical run or every 12 hours, which ever is more frequent.

16.16.2 Limits –

• ICS-A - the absolute value of concentration for all non-spiked analytes must be less than the LOD (unless they are a verified trace impurity from one of the spiked analytes).

• ICS-AB - The analytes in ICS-AB should recover within 20% of the expected value. If the analytes are not present, monitor concentration for possible interferences.

16.16.3 Corrective action – Terminate analysis, locate and correct the problem, reanalyze ICS, reanalyze all affected samples. If corrective action fails, qualify the associated sample data.

17) Data Records Management

See CE-GEN003 and ADM-ARCH.

18) Contingencies for Handling Out-Of-Control Data

If data is produced that is out of control and is not to be re-analyzed due to sample volume restrictions, holding times, or QC controls can not be met, flag and narrate appropriately.

19) Method Performance

19.1 This method was validated through single laboratory studies of accuracy and precision. Refer to the reference method for additional available method performance data.

19.2 Detection and Quantitation Limits are determined for all masses utilized for each type of matrix commonly analyzed. See CE-QA011 for determination and verification of detection and quantitation limits.

19.3 Demonstration of Capability is performed according to the SOP for Training (CE-QA003).


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20) Summary of Changes

• Updated to new ALS format

• Removed copies of standards log and referenced Controlled Forms

• Incorporated Change form for background mass typo.

• Changed the limits for internal standards.

21) References and Related Documents

• USEPA, Test Methods for Evaluating Solid Waste, SW-846, 3rd Edition, Update IV, Method 6020A, Revision 1, February 2007.

• Method 200.8 - Determination of Trace Elements in Waters and Wastes By Inductively Coupled Plasma-Mass Spectrometry, USEPA-EMSL, Revision 5.4, 1994.

• Perkin Elmer Instrument Manuals

• DOD Quality Systems Manual for Environmental Laboratories – Version 4.2, October 2010.

22) Appendix

• DOD Summary

• Table 1 Analytes and Reporting Levels

• Table 2 Recommended Isotopes for Selected Elements

• Table F-8 DOD Data Quality Objectives from QSMv4.2


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DOD SUMMARY

For work for the Department of Defense – the DOD Quality Systems Manual must be followed. The DOD Manual is based on the NELAC Standards with some additional requirements. The exact wording is in Table F-8 (attached). The following are the requirements which are different or additional to routine analysis and must be followed for DOD work:

• The CCB must be less than the LOD.

• The Method Blank must be less than ½ the reporting limit (<RL for common laboratory contaminants).

• Apply J flag to all hits between LOD and LOQ.

• The limits for LCS and MS are 80-120%. All targets are spiked and evaluated.

• The IDL must be less than the LOD. The IDL study is only required by DoD at set-up and after significant change.

• Low Level Check Standard (MRL standard) must be spiked at or below the reporting limit and it must have a recovery of 80-120% of the true value when analyzed at the beginning of the run.

• ICS-A absolute value of concentration for all non-spiked analytes must be <LOD (unless they are a verified trace impurity from one of the spiked analytes).

• Serial Dilution Test

• Only for samples >50 times LOQ

• Corrective Action – If the limits are not met, perform a post digestion spike addition.

• Post digestion spike – Perform when dilution test fails or analyte concentration for all samples <50 times LOQ.

• Method of Standard Additions – use when matrix interference is suspected. Document use in the case narrative.


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TABLE 1

Analyte MRL / LOQ (ug/L) MRL/LOQ (ug/kg) Antimony 1 0.50 Arsenic 1 0.50 Barium 1 0.50

Beryllium 1 0.50 Cadmium 1 0.50 Chromium 2 1.0

Cobalt 1 0.50 Copper 1 0.50 Lead 1 0.50

Manganese 1 0.50 Molybdenum 1 0.50

Nickel 1 0.50 Platinum 1 0.50 Selenium 2 1.0

Silver 1 0.50 Strontium 1 0.50 Thallium 1 0.50 Uranium 1 0.50

Vanadium 2 1.0 Zinc 5 2.5


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DOCUMENT TITLE: METALS DIGESTION, SOILS, SEDIMENTS, AND SLUDGE FOR ICP-AES AND ICP-MS ANALYSIS

REFERENCED METHOD: EPA SW846 3050B SOP ID: MET-3050

REV. NUMBER: 5 EFFECTIVE DATE: 11/4/13


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Metals Digest for Soils MET-3050, Rev 5 Effective: 11/4/13 Page i of i



TABLE OF CONTENTS 1) Scope and Applicability .............................................................................................................. 1 2) Summary of Procedure ............................................................................................................... 1 3) Definitions ................................................................................................................................. 1 4) Health and Safety Warnings........................................................................................................ 2 5) Cautions .................................................................................................................................... 2 6) Interferences.............................................................................................................................. 2 7) Personnel Qualifications and Responsibilities ............................................................................. 2 8) Sample Collection, Preservation and Storage .............................................................................. 3 9) Equipment and Supplies............................................................................................................. 3 10) Standards and Reagents............................................................................................................. 4 11) Method Calibration .................................................................................................................... 5 12) Sample Preparation .................................................................................................................... 5 13) Troubleshooting ........................................................................................................................ 6 14) Data Acquisition ........................................................................................................................ 6 15) Calculation and Data Reduction Requirements............................................................................ 6 16) Quality Control, Acceptance Criteria, and Corrective Action ........................................................ 7 17) Data Records Management......................................................................................................... 7 18) Contingencies for Handling Out Of Control Data ........................................................................ 7 19) Method Performance .................................................................................................................. 7 20) Summary of Changes ................................................................................................................. 7 21) References and Related Documents............................................................................................ 7 22) Appendix ................................................................................................................................... 7


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Metals Digest for Soils MET-3050, Rev. 5 Effective: 11/4/13 Page 1 of 9



METALS DIGESTION, SOILS, SEDIMENTS, AND SLUDGE FOR ICP-AES AND ICP-MS ANALYSIS


Method 3050 is an acid digestion procedure used to prepare matrices such as soils, sludges, or sediments for analysis by ICP-AES or ICP- MS using SW846 methods 6010 and 6020.


A representative aliquot of sample is digested in nitric acid and hydrogen peroxide (and Hydrochloric for ICP-AES). Hydrochloric acid is used as a final reflux acid for ICP-AES analyses. Nitric Acid is used as the final reflux acid for ICP-MS analyses.

3) Definitions

3.1 Laboratory Duplicates - Two aliquots of the same sample taken in the laboratory and analyzed separately with identical procedures. Analyses of duplicates indicates precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.

3.2 Laboratory Control Sample (LCS) - An aliquot of a purchased soil with known quantities of the method analytes. If the purchased soil (LCSS) does not contain all of the target elements needed, the laboratory prepares an LCS with the missing elements by spiking Teflon chips. The LCS is analyzed exactly like a sample, and its purpose is to determine whether the methodology is in control and whether the laboratory is capable of making accurate and precise measurements.

3.3 Matrix Spike - An aliquot of an environmental sample to which known quantities of the method analytes are added in the laboratory. The matrix spike is analyzed exactly like a sample, and its purpose is to determine whether the sample matrix contributes bias to the analytical results.

3.4 Method Blank (MB) - An aliquot of reagent water or other blank matrices that are treated exactly as a sample from digestion to analysis including exposure to all glassware, equipment, solvents, reagents, and internal standards that are used with other samples. The MB is used to determine if method analytes or other interferences are present.

3.5 Digestion Batch - A digestion batch is no more than 20 samples of the same matrix digested as a unit per day. See ADM-BATCH.

3.6 Limit of Detection (LOD) – An estimate of the minimum amount of a substance that an analytical process can reliably detect. An LOD is analyte- and matrix-specific and may be laboratory – dependent.

3.7 Limit of Quantitation (LOQ) – The minimum levels, concentrations, or quantities of a target that can be reported with a specified degree of confidence.


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4.1 All appropriate safety precautions for handling reagents and samples must be taken when performing this procedure. This includes the use of personnel protective equipment, such as, safety glasses, lab coat and the correct gloves.

4.2 Chemicals, reagents, and standards must be handled as described in the company safety policies, approved methods and in the MSDSs where available. Refer to the Environmental Health and Safety Manual and the appropriate MSDS prior to beginning this method.

4.3 Nitric and Hydrochloric Acids are used in this method. These acids are extremely corrosive and care must be taken while handling them. A face shield should be used while pouring acids. And safety glasses should be worn while working with the solutions. Lab coat and gloves should always be worn while working with these solutions.

4.4 Waste Management and Pollution Prevention

4.4.1 It is the laboratory’s practice to minimize the amount of acids and reagents used to perform this method wherever feasible. Standards are prepared in volumes consistent with methodology and only the amount needed for routine laboratory use is kept on site. The threat to the environment from solvent and reagents used in this method can be minimized when disposed of properly.

4.4.2 The laboratory will comply with all Federal, State and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions as specified in the EH&S Manual.

4.4.3 For further information refer to SMO-SPLDIS.

5) Cautions

5.1 All hoods in the Metals Prep Lab are wiped down once a week with DI water. The tops of all digestion hot plates are wiped down daily.

6) Interferences

6.1 Elements bound in silicate structures are not normally dissolved by this method. Such bound elements would not be mobile in the environment and are not normally of interest.

6.2 See appropriate analysis SOP for applicable interferences


7.1 It is the responsibility of the analyst to perform the analysis according to this SOP and to complete all documentation required for data review. Analysis and interpretation of the results are performed by personnel in the laboratory who have demonstrated the ability to generate acceptable results utilizing this SOP. Final review and sign-off of the data is performed by the department supervisor or designee.

7.2 Training – see CE-QA003.


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8) Sample Collection, Preservation and Storage

For solids and non-aqueous samples, glass or plastic sample containers are acceptable. Typically our lab uses purchased, precleaned 4 or 8 oz glass jars. Samples are to be stored at 0-6°C from collection to digestion. Samples are analyzed within 6 months of sample collection. Additional sample handling policies, storage and custody procedures are in SMO-GEN and SMO-ICOC.


9.1 Hot Plate Digestion

9.1.1 Digestion vessel = 250 and 100 mL beakers

9.1.2 Ribbed watch glasses

9.1.3 Hot plates

9.1.4 Funnels

9.1.5 Filter paper

9.2 Hot Block Digestion

9.2.1 Digestion vessel = Graduated block digestor cups

9.2.2 Reflux cap

9.2.3 Hot Block Digestor with ETR-3200 Controller by Environmental Express, LTD

9.2.4 CPI MOD Block Digestor

9.2.5 Block Digestor Filters.

9.3 Graduated cylinders

9.4 Eppendorf Pipettors –Calibrated according to ADM-PCAL.

9.5 Mortar and pestle

9.6 Tongue depressors


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10.1.1 All of the preparation instructions are general guidelines. Other technical recipes may be used to achieve the same results. Example – a 20 mg/L standard may be made by adding 1 mL of 200 mg/L to 10 mL or may be made by adding 4 mL of 50 mg/L to 10 mL. The preparation depends upon the final volume needed and the initial concentration of the stock. Reasonable dilution technique is used

10.1.2 Vendors and vendors’ products are sometimes listed for the ease of the analyst using this SOP, but products and purchased concentrations are examples only and subject to change at any time. All purchased standards are certified by the vendor. Certificates of Analysis are kept in the department until the standards are no longer being used – at which time they are archived with QA. Certificates of Analysis are available upon request. Purchased standards are routinely checked against an independent source for both analyte identification and analyte concentration.

10.1.3 Standards and Reagent expire per the Expiration Policy (CE-QA012) unless otherwise specified.

10.1.4 All Standards must be traceable using the laboratory lot system (CE-QA007).

10.2 Reagent water – laboratory produced deionized water.

10.3 Purchased Reagents and standards – Store at room temperature.

10.3.1 Concentrated nitric acid (Baker Instra-Analyzed 69-70%): Acid should be demonstrated to be free of impurities at levels which would interfere with sample determinations. Store in the dark.

10.3.2 Concentrated hydrochloric acid (Baker Instra-Analyzed 36.5-38%): Acid should be demonstrated to be free of impurities at levels which would interfere with sample determinations.

10.3.3 Hydrogen peroxide (30%) - H2O2. Should be demonstrated to be free of impurities at levels which would interfere with sample determinations.

10.3.4 ERA Soil Laboratory Control Sample (LCSS) - Concentrations and Performance Acceptance Limits distributed through vendor

10.3.5 Metals spiking solutions – Purchased commercially. See Table 1. All target elements needed for client samples in the batch are added to the LCS and MS.

10.4 LCS – use ERA Soil Laboratory Control Sample (LCSS) as above. If the LCSS does not contain all of the target elements needed, create a second LCS sample and spike Teflon chips with the elements missing from the ERA Soil (see Table 1 for appropriate spiking solutions). Digest as a sample.

10.5 MS – Add appropriate spiking solutions (see Table 1) to client sample prior to the addition of heat or reagents. Digest as a sample.

10.6 Method Blank – Digest Teflon chips as a sample.


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11.1 The uniformity of the temperature of the hotplates and hotblocks is monitored by randomly moving a temperature blank around to different positions with each run. The temperature blank is DI in a digestion vessel and the temperature is read with a thermometer held in the DI when the samples should be at the required temperature. If positions become unreliable (not within the required temperature of digestion), those positions must not be used and the unit should be serviced or replaced.

11.2 The graduations on the hot block cups are verified for volume whenever a new lot number of cups is received. To verify the volume, tare a cup on a toploader balance, add DI to the desired graduation (all graduations used for measuring volume must be checked) and record the mass. Repeat on 10 cups. The mean mass must be within 3% of the marked volume. The RSD must be ≤ 3%. If criteria is not met, the lot of cups is either rejected and removed from service or a correction factor must be employed

12) Sample Preparation

12.1 Be sure there is a current LOD and the analyst has a current Demonstration of Capability.

12.2 Be sure the hot block cups have been verified for volume. Record the lot number of the cups used in the batch through the Standards Log in LIMS.

12.3 Set the temperature on the Hot Plate or Block Digestor to a temperature that brings the sample temperature to 90-95°C without boiling.

12.4 The Hot Block is on a timer which can be set to turn on and off whenever necessary. To set timer press the timer button and choose the days M-F (Monday through Friday). Then choose the hour and minutes to start and stop the Block Digestor. The temperature of the batch is monitored by randomly placing a vessel with DI in the block or on the hotplate. Record the temperature and the ID of the hotplate or hotblock in the Comments section of the MB on the prep sheet.

12.5 Label digestion vessel with appropriate sample IDs for digestion.

12.6 See ADM-SPLPREP for instructions of how to homogenize and subsample and how to handle standing water and extraneous materials. Make note of any special sample handling in the comments section of the prep sheet.

12.7 Weigh (to the nearest 0.01g) 1.00g to 1.05g of sample into the digestion vessel. For sludges and sediments that have a high moisture content, use more sample. The goal is to use about 1g of dry weight sample. Record the sample weight, sample color, and sample texture directly into LIMS in real time – do not handwrite on anything to be later entered. Add the appropriate spiking solutions (see Table 1) directly onto the designated spike sample prior to addition of reagents. Record the spike volumes, spiking solutions, and reagents directly into LIMS.

12.8 Unless specified by project or state requirements, add the following to each sample and QC sample: 10 mL of 1:1 HNO3 and, for ICP-AES and Silver or Antimony by ICP-MS, add 1.0 mL of 1:1 HCl. Place digestion vessel on hotplate or in hotblock. Cover with a ribbed watch glass or reflux cap and reflux for 15 minutes. The sample temperature should be 90-95oC. Allow the sample to cool. Add 5 mL of concentrated HNO3, cover and reflux for 30 minutes. Repeat the addition of 5 mL of HNO3 and reflux to 5 mL. Do not allow the sample to go to dryness. CAUTION: Do not boil. Antimony is easily lost by volatilization.


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12.9 Cool the sample and add 2 mL of DI and 3 mL of 30% H2O2. Cover and heat to start the peroxide reaction. Care must be taken to ensure that losses do not occur due to excessive effervescence. Heat until effervescence subsides and cool the digestion vessel.

12.10 If the effervescence does not subside, add 3 mLs of hydrogen peroxide with warming to each of the samples (including blanks and LCSs) in the batch. If necessary, continue to add 30% H2O2 in 1 mL aliquots with warming until the effervescence is minimal, or until the general sample appearance is unchanged. Do not add more than 10ml of 30% H2O2.

12.11 If the sample is being prepared for analysis by ICP-AES or Silver or Antimony by ICP-MS, add 10 mL 1:1 HCL. If the sample is being prepared for analysis by ICP-MS, no HCl is added and the sample is evaporated to approximately 5 mL.

12.12 Cover and reflux the ICP-AES and Silver or Antimony by ICP-MS samples for 15 minutes without boiling. Allow to cool.

12.13 Prepare filters by rinsing with 1:1 nitric acid and DI.

12.14 Filter if particulates are suspended. If particulates have settled, no filtering is necessary. Filtering is usually required if analyzed on the same day as digestion. If filtering, record the lot number of the filters through the Standards Log in LIMS. If the entire batch is filtered, also filter the QC samples. If only some of the samples are filtered, note which samples are filtered in the comments section of the benchsheet and filter an undigested LCS and MB to demonstrate the acceptability of the filters.

12.15 Quantitatively transfer the digestate to a graduated cylinder by pouring the sample through a prepared filter into the cylinder and rinsing the beaker and watch glass or reflux cap with DI into the filter. Rinse the filter with DI. If not filtering, quantitatively transfer digestate to a graduated cylinder rinsing beaker with DI. All samples are diluted to 100 mL with DI. Document the final volume in LIMS. Pour into a labeled B-cup.

12.16 Print out one copy of the Preparation Information Benchsheet. The prep sheets are reviewed and signed by a peer or supervisor within 48 hours of preparation. This prep sheet is filed in the appropriate binder (logbook). A copy remains with the samples through analysis. Copies made for client folders are to include all review signatures.

13) Troubleshooting

None


Preparation volumes are entered manually into the LIMS Prep Sheet and are used to calculate final results

15) Calculation and Data Reduction Requirements

Data must be reviewed by the analyst and a peer (supervisor or qualified analyst) using a Data Quality Checklist before the results are validated and reported to the client. Further data review policies and procedures are discussed in ADM-DREV.


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16.1 LCS - Digest one laboratory control sample (LCS) per digestion batch.

16.2 MB - Digest one Method blank per digestion batch.

16.3 DUP/MS - Digest one spiked sample and one duplicate sample (or matrix spiked duplicate if specified by client) with each digestion batch.

16.4 See appropriate analytical SOP for applicable QC limits and corrective action.


See CE-GEN003 and ADM-ARCH

18) Contingencies for Handling Out Of Control Data



• Detection and Quantitation limits are determined according to the requirements in CE-QA011. The supporting information is filed with the QA office.

• Demonstration of Capability is performed according to CE-QA003.


• Updated to ALS format – removed CAS throughout

• Removed references to GFAA methods and CLP

• Incorporated change form for reduction of HCl


• “Test Methods For Evaluating Solid Waste, Physical/Chemical Methods”. EPA SW846, Third Edition, December 1996.

22) Appendix

• Table 1 Spike Concentrations

• Digestion Log Benchsheet

• SW846 Method 3050 Flow Chart


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Table 1 Spiking Concentrations for LCS and MS Samples SPIKE SOLUTION A 1.00ml Spk A to Final Vol of 100ml

Metal Conc. (ug/mL) Metal Conc. (ug/mL) AL 200 NI 50 AS 4 SE 1 BA 200 AG 5 BE 5 TL 200 CD 5 V 50 CR 20 ZN 50 CO 50 B 100 CU 25 CA 200 FE 100 MG 200 PB 50 NA 2000 MN 50 K 2000

SPIKE SOLUTION B 1.00ml Spk B to Final Vol of 100ml Metal Conc. (ug/mL) Metal Conc. (ug/mL)

SB 50 TI 50 MO 50 - -

INDIVIDUAL METALS

0.10ml Spk. to Final Volume of 100ml

INDIVIDUAL METALS

0.5ml Spk. to Final Volume of 100ml

Metal Conc. (ug/mL) Metal Conc. (ug/mL) SE 1000 SN 1000


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SW846 Method 3050 Flow Chart

____________________________________________________ Soils, Sediments and Sludges

____________________________________________________

Mix sample. Weigh 1.00-1.05g of sample. Spike if needed.

Add 5mL conc. HNO3 and reflux for 30 min. Repeat.

Evaporate to 5mL and cool.

Add 2mL DI and 3mL 30% H2O2. Warm gently to start effervescence.

If efferv. doesn’t subside, add 3mL portion of 30% H2O2 (followed by warming). Add 1 mL portions until efferv subsides. Don’t add

more than a total of 10mL 30% H2O2.

ICP-AES Type of Digest

ICP-MS

Add 10mL (1:1) HNO3 and for ICP only add 1.5 mL 1:1 HCl, mix to a slurry and cover

Gently reflux 15min. and cool

Transfer or Filter into grad cylinder,

collecting DI rinses

Dilute to 100mL with DI water

Evaporate to approximately 5 mL and cool

Add 10 mL 1:1 HCl Reflux 15 min.


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DOCUMENT TITLE: DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA EMISSION

SPECTROSCOPY (ICP) REFERENCED METHOD: EPA 200.7 AND SW 846 6010C

SOP ID: MET-200.7 REV. NUMBER: 14


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Metals by ICP MET-200.7, Rev 14 Effective: 11/4/13 Page i of i



TABLE OF CONTENTS 1) Scope and Applicability .............................................................................................................. 1 2) Summary of Procedure ............................................................................................................... 1 3) Definitions ................................................................................................................................. 2 4) Health and Safety Warnings........................................................................................................ 4 5) Cautions .................................................................................................................................... 5 6) Interferences.............................................................................................................................. 5 7) Personnel Qualifications and Responsibilities ............................................................................. 9 8) Sample Collection, Preservation, and Storage ............................................................................. 9 9) Equipment and Supplies........................................................................................................... 10 10) Standards and Reagents........................................................................................................... 11 11) Method Calibration .................................................................................................................. 13 12) Sample Preparation and Analysis .............................................................................................. 14 13) Troubleshooting ...................................................................................................................... 15 14) Data Acquisition ...................................................................................................................... 15 15) Calculations and Data Reduction Requirements ........................................................................ 16 16) Quality Control, Acceptance Criteria, and Corrective Action ...................................................... 16 17) Data Records Management....................................................................................................... 20 18) Contingencies for Handling Out Of Control Data ...................................................................... 20 19) Method Performance ................................................................................................................ 20 20) Summary of Changes ............................................................................................................... 21 21) References and Related Documents.......................................................................................... 21 22) Appendix ................................................................................................................................. 21

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Metals by ICP MET-200.7, Rev. 14 Effective: 11/4/13 Page 1 of 28



DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA EMISSION SPECTROSCOPY (ICP)


This SOP uses EPA methods 200.7 and 6010C for the determination of trace metals in solution by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The method is applicable to all of the elements listed in Table 1. All matrices, including ground water, aqueous samples, TCLP and EP extracts, industrial and organic wastes, soils, sludges, sediments, and other solid wastes, require digestion prior to analysis.

Detection limits, sensitivity, and the optimum and linear concentration ranges of the elements can vary with the wavelength, spectrometer, matrix and operating conditions. The Reporting Limits are listed in Table 1. The reporting limit may be adjusted if required for specific project requirements, however, the capability of achieving other reporting limits must be demonstrated.


Sample preparation and digestion is found in the appropriate extraction and digestion SOPs. Examples include MET-3010A, MET-3050B, MET-TCLP, MET-TZHE, MET-SPLP, and MET-SPLPZHE.

This method uses multiple elemental determinations by ICP-AES using sequential or simultaneous optical systems and both axial and radial viewing of the plasma (dual view). The instrument measures characteristic emission spectra by optical spectrometry. Samples are nebulized and the resulting aerosol is transported to the plasma torch. Element-specific emission spectra are produced by a radio-frequency inductively coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of the emission lines are monitored by photosensitive devices. Background correction is required for trace element determination. Background must be measured adjacent to analyte lines on samples during analysis. The position selected for the background-intensity measurement, on either or both sides of the analytical line, will be determined by the complexity of the spectrum adjacent to the analyte line. In one mode of analysis the position used should be as free as possible from spectral interference and should reflect the same change in background intensity as occurs at the analyte wavelength measured. Background correction is not required in cases of line broadening where a background correction measurement would actually degrade the analytical result. The possibility of additional interferences named in the Interferences Section should also be recognized and appropriate corrections made.

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3) Definitions

3.1 Initial Calibration - analysis of analytical standards for a series of different specified concentrations; used to define the linearity and dynamic range of the response of the detector to the element.

3.2 Calibration Standard (CAL) - A solution prepared from the dilution of stock standard solutions. The CAL solutions are used to calibrate the instrument response with respect to analyte concentration.

3.3 Dissolved Analyte - The concentration of analyte in an aqueous sample that will pass through a 0.45 μm membrane filter assembly prior to sample acidification.

3.4 Initial Calibration Verification (ICV) (also called Second Source Calibration Verification) – ICV solutions are made from a stock solution which is different from the stock used to prepare calibration standards and is used to verify the validity of the initial calibration.

3.5 Continuing Calibration Verification Standard (CCV) - A standard analyzed at specified intervals and used to verify the ongoing validity of the instrument calibration. For the LLCCV, see MRL Standard below.

3.6 Matrix Spike (MS) - An aliquot of an environmental sample to which known quantities of all of the elements of client interest are added in the laboratory. The matrix spike is analyzed exactly like a sample, and its purpose is to determine whether the sample matrix contributes bias to the analytical results in a given client matrix.

3.7 Duplicate (DUP) - A laboratory duplicate. Two aliquots of the same sample taken in the laboratory and analyzed separately with identical procedures. Analysis of duplicates indicates precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.

3.8 Laboratory Control Sample (LCS) – A matrix blank spiked with all of the elements of client interest. The LCS is analyzed exactly like a sample, and its purpose is to determine whether the methodology is in control and whether the laboratory is capable of making accurate measurements. LCS-Soil is purchased from a vendor.

3.9 Method Blank (MB) - An aliquot of reagent water or other blank matrix that is treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents, and internal standards that are used with other samples. The MB is used to determine if method analytes or other interferences are present in the laboratory environment, reagents, or apparatus.

3.10 Instrument Blank (ICB/CCB) - The instrument blank (also called initial or continuing calibration blank) is a volume of reagent water acidified with the same acid matrix as in the calibration standards. This blank is the zero standard and has a reagent composition identical to the digestates. The purpose of the ICB/CCB is to determine the levels of contamination associated with the instrumental analysis.

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3.11 Batch – a group of no more than 20 samples analyzed together on the same day with the same reagents. See the SOP for Batches and Sequences (ADM-BATCH) for more detail.

3.12 Calibration Blank - A volume of reagent water acidified with the same acid matrix as in the calibration standards. The calibration blank is a zero standard and is used to calibrate the ICP instrument.

3.13 Instrument Detection Limit (IDL) - The concentration equivalent to a signal due to the analyte which is equal to three times the standard deviation of a series of 21 replicate measurements of a low standard’s signal at the same wavelength.

3.14 Internal Standard - Pure analyte(s) added to a sample, extract, or standard solution in known amount(s) and used to measure the relative responses of other method analytes that are components of the same sample or solution. The internal standard must be an analyte that is not a sample component.

3.15 Linear Range - The concentration range over which the instrument response to an analyte is linear.

3.16 Limit of Detection (LOD) – An estimate of the minimum amount of a substance that an analytical process can reliably detect. An LOD is analyte- and matrix-specific and may be laboratory – dependent. For DOD, the smallest amount or concentration of a substance that must be present in a sample in order to be detected at a high level of confidence (99%). At the LOD, the false negative rate (Type II error) is 1%.

3.17 Limit of Quantitation (LOQ) – The minimum levels, concentrations, or quantities of a target that can be reported with a specified degree of confidence. For DOD, the lowest concentration that produces a quantitative result within specified limits of precision and bias. The LOQ shall be set at or above the concentration of the lowest initial calibration standard.

3.18 Plasma Solution - A solution that is used to determine the optimum height above the work coil for viewing the plasma.

3.19 Interference Check Solution (ICS) - A solution of selected method analytes of higher concentrations which is used to evaluate the procedural routine for correcting known interelement spectral interferences with respect to a defined set of method criteria.

3.20 MRL Standard – Standard prepared with a known concentration of elements to check accuracy at the quantitation limit. This is also known as Low-level calibration check standard (LLCCV or LLICV). This standard is not digested.

3.21 LOQ Standard – also called LLQC – Standard prepared at the LOQ that undergoes digestion and preparation procedures.

3.22 HLCCV1 – A standard prepared at the bench at a high concentration to encompass the range of the samples being analyzed. This standard is used to assess accuracy at the high end of the calibration curve.

3.23 HLCCV2 – A standard prepared slightly higher than the calibration range for metals. This is an “upper range limit” standard used to verify the upper limit of the linear dynamic range of the instrument.

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3.24 Matrix - the predominant material, component, or substrate (e.g., surface water, drinking water, etc.) of which the sample to be analyzed is composed.

3.25 Relative Percent Difference (RPD) – The absolute value of the difference of two values divided by the average of the same two values. Used to compare the precision of the analysis. The result is always a positive number.

3.26 Interelement Correction Factors (IECs) - factors that the instrument uses to compensate for spectral overlap when analyzing samples with complex spectra.


4.1 All appropriate safety precautions for handling solvents, reagents and samples must be taken when performing this procedure. This includes the use of personal protective equipment, such as safety glasses, lab coat and the correct gloves.

4.2 Chemicals, reagents and standards must be handled as described in the Company safety policies, approved methods and in MSDSs where available. Refer to the Environmental, Health and Safety Manual and the appropriate MSDS prior to beginning this method.

4.3 Hydrochloric and Nitric Acid are used in this method. These acids are extremely corrosive and care must be taken while handling them. A face shield should be used while pouring acids. And safety glasses should be worn while working with the solutions. Lab coat and gloves should always be worn while working with these solutions.

4.4 The use of pressurized gases is required for this procedure. Care should be taken when moving cylinders. All gas cylinders must be secured to a wall or an immovable counter with a chain or a cylinder clamp at all times. Sources of flammable gases (e.g., pressurized hydrogen) should be clearly labeled.


4.6 High Voltage - The power unit supplies high voltage to the RF generator which is used to form the plasma. The unit should never be opened. Exposure to high voltage can cause injury or death.

4.7 UV Light - The plasma when lit is a very intense light, and must not be viewed with the naked eye. Protective lenses are in place on the instrument. Glasses with special protective lenses are available.

4.8 Waste Management And Pollution Prevention

It is the laboratory’s practice to minimize the amount of acids and reagent used to perform this method wherever feasible. Standards are prepared in volumes consistent with methodology and only the amount needed for routine laboratory use is kept on site. The threat to the environment from solvent and reagents used in this method can be minimized when disposed of properly.

The laboratory will comply with all Federal, State and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions as specified in the EH&S Manual..

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Samples with analyte concentrations exceeding TCLP regulatory limits are disposed of as hazardous waste, see SOP SMO-SPLDIS.

5) Cautions

5.1 Typical preventive maintenance measures include, but are not limited to, the following items:

• Changing the pump tubing as needed

• Empty waste container, as needed

• Cleaning the nebulizer, spray chamber, and torch, as needed

• Replace water and vacuum filters, as needed

6) Interferences

6.1 There are several types of interferences by the ICPs: Spectral interferences can be from an overlap of spectral lines, background points or background from line emissions of high concentration elements. Physical interferences are effects associated with the sample introduction process, example high dissolved solids buildup on the nebulizer tip. Chemical interferences caused by the sample matrix itself. IECs aid in eliminating some of these interferences. IECs are interelement correction factors that the instrument uses to compensate for spectral overlap when analyzing samples with complex spectra. The following is the text from Method 6010B Section 3.0. Similar text is found in Method 200.7 and 6010C. Not all of the items may be applicable to this laboratory’s instruments or procedures.

6.2 Spectral interferences are caused by background emission from continuous or recombination phenomena, stray light from the line emission of high concentration elements, overlap of a spectral line from another element, or unresolved overlap of molecular band spectra.

6.3 Background emission and stray light can usually be compensated for by subtracting the background emission determined by measurements adjacent to the analyte wavelength peak. Spectral scans of samples or single element solutions in the analyte regions may indicate when alternate wavelengths are desirable because of severe spectral interference. These scans will also show whether the most appropriate estimate of the background emission is provided by an interpolation from measurements on both sides of the wavelength peak or by measured emission on only one side. The locations selected for the measurement of background intensity will be determined by the complexity of the spectrum adjacent to the wavelength peak. The locations used for routine measurement must be free of off-line spectral interference (interelement or molecular) or adequately corrected to reflect the same change in background intensity as occurs at the wavelength peak. For multivariate methods using whole spectral regions, background scans should be included in the correction algorithm. Off-line spectral interferences are handled by including spectra on interfering species in the algorithm.

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6.4 To determine the appropriate location for off-line background correction, the user must scan the area on either side adjacent to the wavelength and record the apparent emission intensity from all other method analytes. This spectral information must be documented and kept on file. The location selected for background correction must be either free of off-line interelement spectral interference or a computer routine must be used for automatic correction on all determinations. If a wavelength other than the recommended wavelength is used, the analyst must determine and document both the overlapping and nearby spectral interference effects from all method analytes and common elements and provide for their automatic correction on all analyses. Tests to determine spectral interference must be done using analyte concentrations that will adequately describe the interference. Normally, 100 mg/L single element solutions are sufficient; however, for analytes such as iron that may be found at high concentration, a more appropriate test would be to use a concentration near the upper analytical range limit.

6.5 Spectral overlaps may be avoided by using an alternate wavelength or can be compensated by equations that correct for interelement contributions. Instruments that use equations for interelement correction require the interfering elements be analyzed at the same time as the element of interest. When operative and uncorrected, interferences will produce false positive determinations and be reported as analyte concentrations. More extensive information on interfering effects at various wavelengths and resolutions is available in reference wavelength tables and books. Users may apply interelement correction equations determined on their instruments with tested concentration ranges to compensate (off line or on line) for the effects of interfering elements. Some potential spectral interferences observed for the recommended wavelengths are given in Table 2. For multivariate methods using whole spectral regions, spectral interferences are handled by including spectra of the interfering elements in the algorithm. The interferences listed are only those that occur between method analytes. Only interferences of a direct overlap nature are listed. These overlaps were observed with a single instrument having a working resolution of 0.035 nm.

6.6 When using interelement correction equations, the interference may be expressed as analyte concentration equivalents (i.e. false analyte concentrations) arising from 100 mg/L of the interference element. For example, assume that As is to be determined (at 193.696 nm) in a sample containing approximately 10 mg/L of Al. According to Table 2, 100 mg/L of Al would yield a false signal for As equivalent to approximately 1.3 mg/L. Therefore, the presence of 10 mg/L of Al would result in a false signal for As equivalent to approximately 0.13 mg/L. The user is cautioned that other instruments may exhibit somewhat different levels of interference than those shown in Table 2. The interference effects must be evaluated for each individual instrument since the intensities will vary.

6.7 Interelement corrections will vary for the same emission line among instruments because of differences in resolution, as determined by the grating, the entrance and exit slit widths, and by the order of dispersion. Interelement corrections will also vary depending upon the choice of background correction points. Selecting a background correction point where an interfering emission line may appear should be avoided when practical. Interelement corrections that constitute a

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major portion of an emission signal may not yield accurate data. Users should not forget that some samples may contain uncommon elements that could contribute spectral interferences.

6.8 The interference effects must be evaluated for each individual instrument whether configured as a sequential or simultaneous instrument. For each instrument, intensities will vary not only with optical resolution but also with operating conditions (such as power, viewing height and argon flow rate). When using the recommended wavelengths, the analyst is required to determine and document for each wavelength the effect from referenced interferences (Table 2) as well as any other suspected interferences that may be specific to the instrument or matrix. The analyst is encouraged to utilize a computer routine for automatic correction on all analyses.

6.9 Users of sequential instruments must verify the absence of spectral interference by scanning over a range of 0.5 nm centered on the wavelength of interest for several samples. The range for lead, for example, would be from 220.6 to 220.1 nm. This procedure must be repeated whenever a new matrix is to be analyzed and when a new calibration curve using different instrumental conditions is to be prepared. Samples that show an elevated background emission across the range may be background corrected by applying a correction factor equal to the emission adjacent to the line or at two points on either side of the line and interpolating between them. An alternate wavelength that does not exhibit a background shift or spectral overlap may also be used.

6.10 If the correction routine is operating properly, the determined apparent analyte(s) concentration from analysis of each interference solution should fall within a specific concentration range around the calibration blank. The concentration range is calculated by multiplying the concentration of the interfering element by the value of the correction factor being tested and divided by 10. If after the subtraction of the calibration blank the apparent analyte concentration falls outside of this range in either a positive or negative direction, a change in the correction factor of more than 10% should be suspected. The cause of the change should be determined and corrected and the correction factor updated. The interference check solutions should be analyzed more than once to confirm a change has occurred. Adequate rinse time between solutions and before analysis of the calibration blank will assist in the confirmation.

6.11 When interelement corrections are applied, their accuracy should be verified, daily, by analyzing spectral interference check solutions. If the correction factors or multivariate correction matrices tested on a daily basis are found to be within the 20% criteria for 5 consecutive days, the required verification frequency of those factors in compliance may be extended to a weekly basis. Also, if the nature of the samples analyzed is such they do not contain concentrations of the interfering elements at ± one reporting limit from zero, daily verification is not required. All interelement spectral correction factors or multivariate correction matrices must be verified and updated every six months or when an instrumentation change, such as in the torch, nebulizer, injector, or plasma conditions occurs. Standard solution should be inspected to ensure that there is no contamination that may be perceived as a spectral interference.

6.12 When interelement corrections are not used, verification of absence of interferences is required.

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6.13 One method is to use a computer software routine for comparing the determinative data to limits files for notifying the analyst when an interfering element is detected in the sample at a concentration that will produce either an apparent false positive concentration, (i.e., greater than) the analyte instrument detection limit, or false negative analyte concentration, (i.e., less than the lower control limit of the calibration blank defined for a 99% confidence interval).

6.14 Another method is to analyze an Interference Check Solution(s) which contains similar concentrations of the major components of the samples (>10 mg/L) on a continuing basis to verify the absence of effects at the wavelengths selected. These data must be kept on file with the sample analysis data. If the check solution confirms an operative interference that is > 20% of the analyte concentration, the analyte must be determined using (1) analytical and background correction wavelengths (or spectral regions) free of the interference, (2) by an alternative wavelength, or (3) by another documented test procedure.

6.15 Physical interferences are effects associated with the sample nebulization and transport processes. Changes in viscosity and surface tension can cause significant inaccuracies, especially in samples containing high dissolved solids or high acid concentrations. If physical interferences are present, they must be reduced by diluting the sample or by using a peristaltic pump, by using an internal standard or by using a high solids nebulizer. Another problem that can occur with high dissolved solids is salt buildup at the tip of the nebulizer, affecting aerosol flow rate and causing instrumental drift. The problem can be controlled by wetting the argon prior to nebulization, using a tip washer, using a high solids nebulizer or diluting the sample. Also, it has been reported that better control of the argon flow rate, especially to the nebulizer, improves instrument performance: this may be accomplished with the use of mass flow controllers.

6.16 Chemical interferences include molecular compound formation, ionization effects, and solute vaporization effects. Normally, these effects are not significant with the ICP technique, but if observed, can be minimized by careful selection of operating conditions (incident power, observation position, and so forth), by buffering of the sample, by matrix matching, and by standard addition procedures. Chemical interferences are highly dependent on matrix type and the specific analyte element.

6.17 Memory interferences result when analytes in a previous sample contribute to the signals measured in a new sample. Memory effects can result from sample deposition on the uptake tubing to the nebulizer and from the build up of sample material in the plasma torch and spray chamber. The site where these effects occur is dependent on the element and can be minimized by flushing the system with a rinse blank between samples. The possibility of memory interferences should be recognized within an analytical run and suitable rinse times should be used to reduce them. The rinse times necessary for a particular element must be estimated prior to analysis. This may be achieved by aspirating a standard containing elements at a concentration ten times the usual amount or at the top of the linear dynamic range. The aspiration time for this sample should be the same as a normal sample analysis period, followed by analysis of the rinse blank at designated intervals. The length of time required to reduce analyte signals to within a factor of two of the method detection limit should be

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noted. Until the required rinse time is established, this method suggests a rinse period of at least 60 seconds between samples and standards. If a memory interference is suspected, the sample must be reanalyzed after a rinse period of sufficient length. Alternate rinse times may be established by the analyst based upon their DQOs.

6.18 Users are advised that high salt concentrations can cause analyte signal suppressions and confuse interference tests. If the instrument does not display negative values, fortify the interference check solution with the elements of interest at 0.5 to 1 mg/L and measure the added standard concentration accordingly. Concentrations should be within 20% of the true spiked concentration or dilution of the samples will be necessary. In the absence of measurable analyte, overcorrection could go undetected if a negative value is reported as zero.

6.19 The dashes in Table 2 indicate that no measurable interferences were observed even at higher interfering concentrations. Generally, interferences were discernible if they produced peaks, or background shifts, corresponding to 2 to 5% of the peaks generated by the analyte concentrations.


It is the responsibility of the analyst to perform the analysis according to this SOP and to complete all documentation required for data review. Analysis and interpretation of the results are performed by personnel in the laboratory who have demonstrated the ability to generate acceptable results utilizing this SOP. Final review and sign-off of the data is performed by the department supervisor or designee.

Training – see CE-QA003.

8) Sample Collection, Preservation, and Storage

8.1 Solid samples require no preservation prior to digestion other than storage at 0-6°C. Sample containers may be glass or plastic. When the laboratory provides the sample containers, the containers are purchased, certified clean glass soil jars with Teflon-lined lids. Samples are analyzed within 6 months of collection.

8.2 For aqueous samples, glass or plastic sample containers are acceptable. When the laboratory provides the sample containers, the containers are purchased, certified clean 250 or 500 mL plastic bottles. Sample volume should be acid preserved with (1+1) nitric acid to pH <2. Samples are held at room temperature (although refrigeration is acceptable also). Samples are analyzed within 6 months of sample collection.

8.3 For the determination of the dissolved elements, the sample must be filtered through a 0.45 μm pore diameter membrane filter at the time of collection or as soon thereafter as practically possible. (Glass or plastic filtering apparatus are recommended to avoid possible contamination. Only plastic apparatus should be used when the determinations of boron and silicon are critical.) Samples should be filtered prior to acidification, because acidification changes the sample (usually by dissolving particulates that would be filtered out). Acidified samples received at the lab that require lab filtration must be noted in the case narrative. See digestion SOPs for filtration procedure.

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8.4 Samples received by the ICP lab as digestates contain nitric and hydrochloric acid. Digestates are stored at room temperature in plastic B-cups or Hot Block Digestion cups.

8.5 Following analysis, digestates are stored until all results have been reviewed. Digestates are diluted and disposed of through the sewer system in approximately 90 days after receipt of sample.

8.6 For more information about custody, sample handling, and storage procedures, see SMO-GEN and SMO-ICOC.



Acquired

Instrument Perkin Elmer 5300DV 077N6051602

Computer Workstation Dell Optiplex GX620 ICP #3

(R-ICP-AES-03) Analytical Software PE ICP WinLab v.3.1

2006

Instrument Perkin Elmer 5300DV 077N6052202

Computer Workstation Dell Optiplex GX620 ICP #4

(R-ICP-AES-04) Analytical Software PE ICP WinLab v.3.1

2010

Instrument Perkin Elmer Optima 8000 078N2072408C

Autosampler AAS S-10 102S12031301

Computer Workstation Lenova Thinkcentre

ICP #5 (R-ICP-AES-05)

Analytical Software

PE ICP WinLab 32 v5.2.0.0612

2013

These instruments are “dual” view – they use axial and radial views simultaneously

9.1 Argon gas supply - high purity

9.2 Volumetric flasks, class A.

9.3 Calibrated adjustable Micropipet with disposable tips. See ADM-PCAL for calibration requirements.

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10.1 Trace metals grade chemicals shall be used in all tests. Each lot of acid used is to be analyzed to demonstrate that it is free of interference before use (see CE-GEN007). Store all acids at room temperature. Acids expire upon manufacturer’s indications or per Expiration Policy if not otherwise indicated.

• Hydrochloric acid (conc.), HCl, and Nitric acid (conc), HNO3. Purchased

commercially.

10.2 Reagent Water. All references to water in this SOP refer to the water produced by the laboratory water system.


10.3.1 All of the preparation instructions are general guidelines. Other technical recipes may be used to achieve the same results. Example – a 20 mg/L standard may be made by adding 1 mL of 200 mg/L to 10 mL or may be made by adding 4 mL of 50 mg/L to 10 mL. The preparation depends upon the final volume needed and the initial concentration of the stock. Reasonable dilution technique is used.

10.3.2 Vendors and vendors’ products are sometimes listed for the ease of the analyst using this SOP, but products and purchased concentrations are examples only and subject to change at any time. All purchased standards are certified by the vendor. Certificates of Analysis are kept in the department until the standards are no longer being used – at which time they are filed with QA. Certificates of Analysis are available upon request. Purchased standards are routinely checked against an independent source for both analyte identification and analyte concentration.

10.3.3 All Standards must be traceable using the laboratory lot system. See the SOP for Making Entries Onto Analytical Records (CE-QA007) for detail.

10.3.4 All standards are prepared from NIST traceable stock standard solutions. Manufacturer’s expiration dates are used to determine viability of standards. Preparatory procedures for standards and QC solutions vary between instruments due to the working ranges. All preparatory information for the standards and QC samples are provided in the Controlled Forms section of the Rochester Intranet in the Metals Standards Logbooks.

10.4 Mixed Calibration Standards are prepared by combining appropriate volumes of the stock solutions in volumetric flasks. Matrix match with the appropriate acid and dilute to 100 mL with water. Calibration standards should be verified using a second source quality control sample (LCS, ICV, or CCV). Calibration standards should be stored at room temperature in glass volumetric flasks with a shelf-life of 7 days.

10.5 Initial and Continuing Calibration Verification (ICV and CCV) Standards are prepared by combining compatible analytes at concentrations equivalent to the midpoint of their respective calibration curves. Matrix match with the

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appropriate acid. The ICV and CCV standards are prepared from a separate source independent from that used in the calibration standards. ICV / CCV standards should be stored at room temperature in glass volumetric flasks with a shelf-life of 48 hours.

10.6 Internal Standard - An internal standard solution consisting of a 10 mg/L solution of Yttrium and Cesium. The apparent concentration is 1.00 mg/L Yttrium. The Yttrium intensity is used by the instrument to ratio the analyte intensity signals for both calibration and quantitation. Cesium is used only as a stabilizer. Store the prepared solutions at room temperature for up to 6 months.

10.7 HLCCV1- The highest calibration standard with the same storage and expiration as the calibration standards.

10.8 HLCCV2 – A standard prepared to verify the linear dynamic range of the instrument. Store at room temperature for up to 14 days.

10.9 LOQ Standards (low level calibration check standards or MRL Standards) are prepared to contain known concentrations of elements at or near the Reporting Limit. LOQ standards should be stored in plastic containers with a shelf-life of 6 months.

10.10 Interference Check Solutions A and AB are prepared to contain known concentrations of interfering analytes that will provide an adequate test of the correction factors. ICSA / ICSAB standards should be stored in plastic containers with a shelf-life of 6 months.

10.11 Laboratory Control Sample and Matrix Spike – see preparation SOP.

10.12 Blanks

10.12.1 Method Blanks –see preparation SOP.

10.12.2 The Calibration Blank is prepared by acidifying reagent water to the same concentrations of acid found in the standards and samples.

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11.1 Follow policies in ADM-ICAL. If these instructions conflict with ADM-ICAL, follow the instructions in this SOP.

11.2 Number of Calibration standards – At least 3 standards and a calibration blank are analyzed for each element at the beginning of the daily sequence. The low standard must be at or below the LOQ. The HLCCV2 standard will define the upper limit of the linear range for the curve.

11.3 Initial Calibration Curve Calculation – Internal Standard Method

11.3.1 Yttrium is added to all samples and QC standards to provide a reference for individual performance of each injection. The software divides the element intensity by the internal standard intensity for each injection and provides a “corrected intensity” for each element on the print-out.

Corrected Intensity = Intensity sample Intensity internal standard

11.3.2 The “corrected intensity” is plotted against concentration using the linear regression equation of a line and forced through zero intensity and zero concentration. This calibration curve assumes that the relationship between concentration (the X values) and intensity (the Y values) is linear and that the following equation describes this relationship:

Y=MX Where: X=concentration Y= corrected intensity M=slope of the calibration curve The intercept is forced to be zero.

Given 2 or more data points, the values for M are calculated using the following equation.

( )

( )∑

∑=

=

12

1

= i

ni

ii

i

n

X

YXM

Where: n=number of standards (includes the blank)

In this equation, the blank is subtracted from all solutions and included in the calculation of the calibration curve

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To avoid bias at the low end of the curve, the curve is forced through zero. Forcing the curve through zero may favor the low end of the curve therefore a MRL Standard (LLCCV) and high level CCV (HLCCV1 and HLCCV2) are analyzed to verify both ends of the curve.

11.4 Acceptance Criteria – the correlation coefficient must be 0.998 or greater for target analytes of interest and the ICV must meet limits (see QC section).

11.5 Corrective Action – if the ICAL does not meet acceptance criteria, correct the problem and recalibrate. The curve must be acceptable before sample analysis begins.


12.1 All samples are digested prior to analysis. Refer to the following Metals Digestion SOPs:

• MET-3010A Metals Digestion, Waters for ICP

• MET-3050B Metals Digestion, Soils, Sediments and Sludges for ICP and GFAA

12.2 Set up the instrument with proper operating parameters established as detailed below. Operating conditions - The analyst should follow the instructions provided in Table 3.

12.3 Before using this procedure to analyze samples, there must be data available documenting initial demonstration of performance. The required data documents the selection criteria of background correction points; linear ranges, and the upper limits of those ranges; the Limits of Detection and Quantitation; and the determination and verification of interelement correction equations or other routines for correcting spectral interferences. This data must be generated using the same instrument, operating conditions and calibration routine to be used for sample analysis. These documented data must be kept on file and be available for review by the data user or auditor. The limits and on-going frequency of these performance demonstrations are provided in the QC Section.

12.4 Turn on power supply for the instrument, computer, printer and light the plasma. Allow instrument to warm-up while preparing the run (typically 45-60 minutes before operation, although only ~10 minutes are necessary). The cooling water and the argon are on when the instrument are on.

12.5 Profile the instrument on a daily basis, or when maintenance is done to align it optically for both horizontal and vertical optimization in either mode. The vendor recommends aspirating a 1.0 ppm source of manganese. Choose the Tools menu/Spectrometer Control/Optimize “Axial” or “Radial” The instrument automatically adjusts the torch viewing position for maximum intensity.

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12.6 Addition of Internal standard -

12.6.1 Pour 40 mL of the calibration blank, the 3 calibration standards, ICV/CCV standards, LOQ, ICSA, and ICSAB into separate 50 mL centrifuge tubes and add 0.80 mL of the 100 mg/L internal standard solution. All other samples, preparation blanks and laboratory control samples are poured up to 10 mL in a 15 mL centrifuge tube and 0.20 mL of internal standard solution is added. This will give an apparent concentration of 1.00 mg/L Yttrium. Other volumes may be used to result in the same concentration.

12.6.2 Internal standards can be added via pump and mixing block. This technique uses a solution of 10 mg/L Y and 10 mg/L Cs.

12.6.3 Place the tubes on the autosampler and program the software to analyze according to the analytical sequence.

12.7 Analytical Sequence – see the Quality Control Section and ADM-BATCH for frequency and requirements.

12.7.1 Rinse the system with the blank solution before the analysis of each sample. The rinse time will be at least one minute, depending upon the instrument. A reduction in rinse time must be demonstrated to be acceptable.

12.8 Sample Analysis and Evaluation

12.8.1 Sensitivity, LOD, LOQ, precision, linear dynamic range, and interference effects must be established for each individual analyte line on each particular instrument. All measurements must be within the instrument linear range where the correction equations are valid.

12.8.2 Samples which exceed the linear range of the instrument (greater than HLCCV2) must be diluted and reanalyzed according to ADM-DIL.

12.8.3 Evaluate QC according to the QC Section. Repeat samples associated with non-compliant QC whenever possible.

13) Troubleshooting

Maintenance log - All Preventive maintenance, as well as instrument repair, should be documented in the appropriate instrument maintenance log. Most routine maintenance and troubleshooting are performed by ALS staff. Other maintenance or repairs may, or may not require factory service, depending upon the nature of the task. Any maintenance performed by outside services must also be documented – either through notes in the log or through documents provided by the service. The log entries will include the date maintenance was performed, symptoms of the problem, serial numbers of major equipment upgrades or replacements. The datafile name of the first acceptable run after maintenance is to be documented in the maintenance log.


Data is electronically transferred from the instrument software to LIMS. The preparation information entered to LIMS is used by LIMS to calculate the final results – see Calculation Section.

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15) Calculations and Data Reduction Requirements

15.1 Calculations: If dilutions were performed, the appropriate factors must be applied to sample values.

15.2 The use of the internal standard is found in the Method Calibration Section.

15.3 Sample Calculation (water)

Conc. (mg/L) =Instrument Reading (mg/L) x Final digestion volume (L) Initial volume (L)

15.4 Sample Calculation (soils)

Conc. (mg/g) = Instrument Reading (mg/L) x Final digestion volume (L) Initial mass (g) x Percent Solids expressed as a decimal


16.1 Instrument values are based on duplicate readings. Precision between the emission readings shall not exceed 20 %RSD. If RSD values exceed 20%, reanalyze the sample. Exception: Analytes <MRL are OK to report with RSD>20%.

16.2 Method Blanks

• Frequency -at least one MB with preparation batch of 20 or fewer samples of the same matrix.

• Limits - MB values must not exceed the LOQ(1/2 LOQ for DOD).

• Corrective Action - Fresh aliquots of the samples must be prepared and analyzed again for affected analytes after the source of the contamination has been corrected and acceptable MB values have been obtained. If detections are greater than the LOQ, the batch needs to be redigested if sample concentration is less than 10 times the concentration found in the method blank. If the sample concentration is less than the LOQ the sample does not require redigestion.

16.3 HLCCV1 – High standard used in curve

• Frequency - analyzed once during daily analysis.

• Limits - Should agree within 10% of the true value.

• Corrective Action - If HLCCV1 is > 10% different the analysis is judged to be out of control and the source of the problem should be identified and resolved before continuing analysis.

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16.4 HLCCV2 – standard slightly higher than calibration for some metals.

• Frequency - Analyzed once during daily analysis.

• Limits - Should agree within 10% of the true value.

• Corrective Action - If out of control, client data above the HLCCV1 should be re-analyzed.

16.5 ICV –

• Frequency - must immediately follow each calibration.

• Limits - ±5% for Method 200.7 and ±10% for Method 6010C.

• Corrective Action – correct the problem and recalibrate the instrument.

16.6 CCV

• Frequency - after every tenth sample, and at the end of the sample run

• Limits - ±10%

• Corrective Action – correct the problem and analyze another CCV. If second CCV fails, recalibrate. Reanalyze affected samples since the last successful CCV. Non-detect samples associated with a high recovery CCV may be reported.

16.7 ICB/CCB

• Frequency – ICB after every ICV and CCB after every CCV (at the beginning and end of the run and after every 10 samples)

• Limits - The results of the calibration blank must be less than the LOQ (less than LOD for DOD).

• Corrective Action - If the limits are not met, terminate the analysis, correct the problem, recalibrate, and reanalyze the samples affected. Non-detect samples associated with a high blank may be reported.

16.8 MS –

• Frequency - one per matrix batch (max. 20 samples) or one per 10 for Method 200.7.

• Limits - within 70-130% (80-120% for DOD) of the actual value or within the documented historical acceptance limits for each matrix. All elements of client interest are evaluated. Sample concentrations greater than four times the spike concentration are not valid and shall not be evaluated.

• Corrective Action - If the matrix spike does not meet these criteria, analyze a Post Digestion Spike. DOD requires project-specific DQOs be examined or contact the client for additional measures. See Table F-7.

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16.9 DUP –

• Frequency - one per matrix batch (max. 20 samples) or one per 10 for Method 200.7

• Limits - A control limit of ± 20% RPD shall be used for original and duplicate samples greater than or equal to 5X the LOQ. A control limit of ± the LOQ shall be used if either the sample or duplicate value is less than 5 times the LOQ.

• Corrective Action – If the DUP does not meet criteria, data will be reported with a qualifier.

16.10 Laboratory Control Sample –

• Frequency – one per matrix batch (max. 20 samples).

• Limits – all elements of client interest are evaluated. Client specific QC recoveries may supercede these limits.

• Waters - Results should be within ± 15% of the true value for method 200.7 and ± 20% for 6010C.

• Soils – Results must be within the limits indicated on the Certificate of Analysis for the soil reference.

• Corrective Action - Outlying recoveries may indicate loss of analyte due to digestion procedures or laboratory contamination. If an LCS is found to be out of the specified limits, recalibrate and reanalyze. If the LCS remains out of control with a low bias, redigestion of the entire batch should occur. If the LCS remains out of control with a high bias, redigestion of all positive results (greater than the LOQ) should occur.

16.11 MRL standard (LLICV/LLCCV) - A standard less than or equal to the LOQ is analyzed

• Frequency - at the beginning and end of each daily analytical run but not before the ICV.

• Limits- There are no limits in the 200.7 method. 6010C requires 70-130%. DOD requires 80-120%.

• Corrective Action - If the limits are not met the analysis is stopped and the instrument is recalibrated.

16.12 Interference Check Samples-

16.12.1 ICSA

• Frequency - at the beginning and end of each daily analytical sequence.

• Limits – less than LOQ (less than 2 times LOQ for metals with LOQ < 10mg/L) – DOD requires that the ICSA be less than the LOD unless they are a verified trace impurity from one of the spiked analytes.

• Corrective Action – terminate analysis; locate and correct problem;

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reanalyze ICS and any associated samples. Samples less than LOQ will be flagged and reported.

16.12.2 ICSAB –

• Frequency – immediately after ICSA

• Limits - The analyte recoveries for the AB solution must fall within 20% of the true value

• Corrective Action - terminate analysis; locate and correct problem; reanalyze ICS and all associated samples unless analytes are not detected in the associated samples or interfering elements are not present at the ICSA level.

16.13 Serial Dilution Test –

• Frequency – one each prep batch or when a new or unusual matrix is encountered. Only applicable to samples with a concentration greater than 50 times the LOQ. If no samples in the prep batch are >50xLOQ, analyze a post-digestion spike.

• Limits - a 5-fold dilution should agree within ± 10% of the original determination.

• Corrective Action – if the results are not within limits, flag the data with a qualifier. For DOD, if the results are not within limits, perform post-digestion spike addition.

16.14 Post Digestion Spike Addition (for 6010C analyses): The spike addition should produce a minimum level of 10 times and a maximum of 100 times the LOQ.

• Frequency – When a dilution test fails, or when no samples have a concentration 50 times the LOQ or if a matrix spike does not yield acceptable results.

• Limits - should be recovered to within 75% to 125% of the known value.

• Corrective action - If the spike is not recovered within the specified limits, a matrix effect has been confirmed and the data must be flagged.

16.15 Instrument Performance

16.15.1 InterElement Correction Factors (IEC)

• Procedure – A calibration curve is analyzed as per instrument specifications. Once completed, individual standards for Al, Ca, Fe, Mg, and Mo (Mo for Optima 4 only) are analyzed. The instrument software then creates an IEC table.

• Frequency - annually, or as needed.

• Limits and corrective action – The ICSA check standard routinely confirms the IECs. If the ICSA is persistently problematic, re-establish IECs.

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16.15.2 Linear Ranges (LR)

• Frequency – Standards (HLCCV1 and HLCCV2) are prepared at the linear range level and analyzed every quarter

• Limits - must be ±5% of true value.

• Corrective Action – If the linear range is too high, lower the linear range and repeat the study.

16.15.3 Instrument Detection Limits (IDL)

• Procedure – Analyze 7 replicates of a low level standard. Repeat twice more for a total of 21 replicates over 3 non-consecutive days.

• Frequency – with initial set-up and after significant change.

• Limits – the calculated IDL must be less than the LOD.

• Corrective Action - If the IDL fails, correct the problem and repeat the study or raise the LOD.

16.15.4 Ongoing verification of detection and quantitation limits is required. See CE-QA011 for requirements.

16.15.5 LOQV (LLQC) – This digested standard spiked at the reporting limit must be analyzed quarterly for DOD (6010C requires “as needed”). The limits are 70-130% for 6010C and LCS limits for DOD. If this QC does not meet these limits, determine the source of the problem. Achieve an acceptable LOQV before continuing.


See CE-GEN003 and ADM-ARCH.

18) Contingencies for Handling Out Of Control Data



Detection and Quantitation limits are determined for all wavelengths utilized for each type of matrix commonly analyzed. See Table 2 for approximate wavelengths. Determine limits according to the requirements in CE-QA011. The supporting information is filed with the QA office.

Demonstration of Capability is performed according to CE-QA003.

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• Updated to new ALS format

• Incorporated SOP change form for reporting non-detects when MRL standard fails high.

• Added ICP #5

• Removed copies of standards log and referenced Controlled Forms

• Updated MRL for Beryllium


• Test Methods For Evaluating Solid Waste, Physical/Chemical Methods. USEPA SW-846, Update IV, December 1996.

• Methods For the Determination of Metals in Environmental Samples Supplement I. USEPA/600/R-94/111, May 1994.

• DOD Quality Systems Manual for Environmental Laboratories – Version 4.2, October 2010.

22) Appendix

• DOD Summary

• Table 1 List of Analytes and Practical Quantitation Limits

• Table 2 Potential Interferences

• Table 3 Recommended Wavelengths and Instrument Specifications

• Table F-7 DOD specific Requirements from DOD QSM Version 4.2 October 2010

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DOD SUMMARY

For work for the Department of Defense – the DOD Quality Systems Manual must be followed. The DOD Manual is based on the NELAC Standards with some additional requirements. The exact wording is in Table F-7. The following are the requirements which are different or additional to routine analysis and must be followed for DOD work:

• The CCB must be less than the LOD.

• The Method Blank must be less than ½ the reporting limit (<RL for common laboratory contaminants).

• Apply J flag to all hits between LOD and LOQ.

• The limits for LCS and MS are 80-120%. All targets are spiked and evaluated.

• The IDL must be less than or equal to the LOD.

• Low Level Check Standard (MRL standard) must be spiked at or below the reporting limit and it must have a recovery of 80-120% of the true value when analyzed at the beginning of the run.

• ICS-A absolute value of concentration for all non-spiked analytes must be <LOD (unless they are a verified trace impurity from one of the spiked analytes).

• Serial Dilution Test Corrective Action – If the limits are not met, perform a post digestion spike addition.

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TABLE 1

TypicalMRL/ LOQ** Analyte Water-Optima Soil

ug/L ug/g Silver 10 1.00 Aluminum 100 10.0 Arsenic 10 1.0 Boron 200 20.0 Barium 20 2.00 Beryllium 3.0 0.300 Calcium 1000 100.0 Cadmium 5.0 0.500 Cobalt 50 5.00 Chromium 10 1.0 Copper 20 2.00 Iron 100 10.0 Potassium 2000 200 Magnesium 1000 100 Manganese 10 1.0 Molybdenum 25 2.50 Sodium 1000 100 Nickel 40 4.00 Lead 50 5.00 Antimony 60 6.00 Selenium 10 1.00 Tin 500 50.0 Titanium 50 5.00 Thallium 10 1.00 Vanadium 50 5.00 Zinc 20 2.00 Lithium 100 10 Silicon 1000 100 Strontium 100 10 Gold 50 Gallium 200 Germanium 100 Hafnium 100 Indium 100 Palladium 100 Platinum 100 Ruthenium 100 Rhenium 100 Tungsten 100 Tantalum 100 Zirconium 100

**See Data Quality Objectives Table for the most current LOQs

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Table 3

Recommended Wavelengths and Instrument Specifications Suggested wavelengths are listed below:

Other wavelengths may be substituted if they can provide the needed sensitivity and are corrected for spectral interference. Because of differences among various makes and models of spectrometers, specific instrument operating conditions cannot be provided. The instrument operating conditions herein are recommended based upon manufacturer’s instrument manuals. Current Method Operating Conditions are as follows, these conditions may vary to optimize the instrument for different analyses:

Analyte Wavelength Ag Silver 328.068 Al Aluminum 308.215 B Boron 249.773 Ba Barium 233.527 Be Beryllium 234.861 Ca Calcium 430.253 Cd Cadmium 226.502 Co Cobalt 228.616 Cr Chromium 267.716 Cu Copper 324.754 Fe Iron 238.863 Mg Magnesium 279.079 Mn Manganese 257.610 Mo Molybdenum 202.030 Na Sodium 330.237 Ni Nickel 231.604 Pb Lead 220.353 Sb Antimony 206.833 Sn Tin 189.933 Ti Titanium 334.941 V Vanadium 292.402 Zn Zinc 206.191 Y Yttrium 371.030

Parameter Radial Plasma Axial Plasma Resolution Fixed Fixed Purge Gas Flow Normal Normal Read Time (min/max sec.) 5/20 5/50 Replicates 2 2 Plasma (L/min) 15 15 Aux. (L/min) 0.5 0.3 Nebulizer Flow (L/min) 0.72 0.56 Power (watts) 1300 1450 Viewing Height (mm) 15 15

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DOCUMENT TITLE: HEXAVALENT CHROMIUM BY ION CHROMATOGRAPHY FOR WATER AND SOIL EXTRACTS

REFERENCED METHOD: EPA 218.6, EPA218.7, SW 7199, EPA 0061, NIOSH 7605

SOP ID: GEN-7199 REV. NUMBER: 6


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Cr6+ by IC GEN-7199, Rev 6 Effective: 10/14/13 Page i of i



TABLE OF CONTENTS 1) Scope And Applicability.............................................................................................................. 1 2) Summary of Procedure ............................................................................................................... 1 3) Definitions ................................................................................................................................. 2 4) Health and Safety Warnings........................................................................................................ 4 5) Cautions .................................................................................................................................... 4 6) Interferences.............................................................................................................................. 4 7) Personnel Qualifications and Responsibilities ............................................................................. 5 8) Sample Containers, Collection, Preservations, and Storage ......................................................... 5 9) Equipment and Supplies............................................................................................................. 8 10) Standards and Reagents............................................................................................................. 9 11) Method Calibration .................................................................................................................. 13 12) Sample Preparation and Analysis .............................................................................................. 14 13) Troubleshooting ...................................................................................................................... 16 14) Data Acquisition ...................................................................................................................... 16 15) Calculation and Data Reduction Requirements.......................................................................... 16 16) Quality Control, Acceptance Limits and Corrective Action ......................................................... 17 17) Data Records Management....................................................................................................... 19 18) Contingencies for Handling Out of Control Data....................................................................... 19 19) Method Performance ................................................................................................................ 19 20) Summary of Changes ............................................................................................................... 19 21) References and Related Documents.......................................................................................... 19 22) Attachments ............................................................................................................................ 20

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Cr6+ by IC GEN-7199, Rev. 6 Effective: 10/14/13 Page 1 of 26



HEXAVALENT CHROMIUM BY ION CHROMATOGRAPHY FOR WATER AND SOIL EXTRACTS

1) Scope And Applicability

1.1 This SOP uses the following methods for the determination of Hexavalent chromium: EPA Method 7199 for water samples and soil extracts; 218.6 for drinking water and other waters; 218.7 for drinking water; NIOSH 7605 for air filter extracts, and 0061 for air impingers.

1.2 Although testing for Hexavalent chromium is not currently regulated in drinking water (except through total chromium limits), the EPA recommended monitoring (Dec 2010) of Hexavalent chromium using 218.6, modified to reach a MDL of 0.02 ug/L (Jan 2011). The EPA released method 218.7 in January of 2012. Method 218.7 has been included in UMCR3 and is to be used for testing of certain public water systems designated by EPA starting January 2013. The UCMR3 MRL is 0.03 ug/L.

1.3 This method may not be useful for the analysis of samples containing high levels of anionic species such as sulfate and chloride, since these species may cause column overload.

1.4 Samples containing high levels of organics or sulfides cause rapid reduction of soluble Cr(VI) to Cr(III).

1.5 This method should be used by analysts experienced in the use of ion chromatography and in the interpretation of ion chromatograms.

1.6 Current reporting limits: Drinking Water Water Soils 218.7 0.03 ug/L NA NA 218.6 0.02 ug/L 0.02 ug/L (LL)

0.01 mg/L (RL) NA

7199 NA 0.01 mg/L 0.40 mg/kg NIOSH 7605 see GEN-N7605

1.7 Current MDLs: Drinking Water Water Soils 218.7 0.01 ug/L NA NA 218.6 0.01 ug/L 0.01 ug/L (LL)

0.001 mg/L (RL) NA

7199 NA 0.001 mg/L 0.026 mg/kg NIOSH 7605 see GEN-N7605


• Waters by 218.6 and 218.7 are preserved with a combined buffer/dechlorinating reagent which complexes free chlorine and increases the pH to a specified value (see Preservation Section). Water samples by 7199 are not chemically preserved with the buffer. Soils are digested by EPA 3060A (GEN-3060A). Air filters are digested by NIOSH 7605 (GEN-N7605).

• A measured volume of the sample is introduced into an ion chromatograph. CrO42- is separated from other matrix components on an anion exchange column. CrO42- is derivatized with 1,5-diphenylcarbazide in a post-column reaction and is detected spectrophotometrically at a wavelength of 530 nm. Cr(VI) is qualitatively identified via retention time, and the concentration of CrO42- in the sample is calculated using the integrated peak area and the external standard technique.

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3) Definitions

3.1 Initial Calibration - analysis of analytical standards for a series of different specified concentrations; used to define the linearity and dynamic range of the response of the system.

3.2 Matrix Spike (MS) - In the matrix spike analysis, a predetermined quantity of standard solution is added to a sample matrix prior to sample preparation and analysis. The purpose of the matrix spike is to evaluate the effects of the sample matrix on the methods used for the analyses. Percent recovery is calculated for the analyte detected. EPA methods 218.6 and 218.7 call the matrix spike a Laboratory Fortified Sample Matrix (LFM or LFSM).

3.3 Soluble Matrix Spike (MS-Sol) - Only applicable to soil preparation batches digested by GEN-3060A. In the soluble matrix spike analysis, a predetermined quantity of a soluble standard solution of the analyte is added to a sample matrix prior to sample digestion and analysis. The purpose of the soluble matrix spike is to evaluate the effects of the sample matrix on the methods used for the analyses. Percent recovery is calculated for the analyte detected

3.4 Insoluble Matrix Spike (MS-Insol) - Only applicable to soil preparation batches digested by GEN-3060A. In the insoluble matrix spike analysis, a predetermined quantity of an insoluble standard of the analyte is added to a sample matrix prior to sample digestion and analysis. The purpose of the insoluble matrix spike is to evaluate the dissolution during the digestion process and effects of the sample matrix on the dissolution. Percent recovery is calculated for the analyte detected.

3.5 Duplicate Sample (DUP) - A laboratory duplicate. The duplicate sample is a separate field sample aliquot that is processed in an identical manner as the sample proper. The relative percent difference between the samples is calculated and used to assess analytical precision. EPA methods 218.6 and 218.7 use the abbreviation LD (Laboratory Duplicate)

3.6 Relative Percent Difference (RPD) – The absolute value of the difference of two values divided by the average of the same two values. Used to compare the precision of the analysis. The result is always a positive number.

3.7 Method Blank (MB) - The method blank is an artificial sample designed to monitor introduction of artifacts into the process. The method blank is carried through the entire preparation and analytical procedure. For waters by 218.7, the MB is the Laboratory Reagent Blank (LRB) or CCB and contains the method preservative.

3.8 Laboratory Control Sample (LCS) - In the LCS or blank spike analysis, a predetermined quantity of standard solution is added to a blank prior to sample analysis. Percent recovery is calculated for the analyte detected. This LCS is a check on the calibration only and has not undergone digestion. The LCS-Insol is a check on the preparation batch.

3.9 Blank Spike (LCS-Insol) – Only applicable to soil preparation batches digested by GEN-3060A. In the LCS-Insol analysis, a predetermined quantity of an insoluble standard solution is added to a blank prior to sample digestion and analysis. Percent recoveries are calculated for the analyte detected.

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3.10 Post Verification Spike (PVS) – The PVS (sometimes referred to as PDS for Post Digestion Spike by New Jersey) analysis is designed to verify that neither a reducing nor a chemical interference is affecting the analysis. In the PVS analysis, a predetermined quantity of a soluble standard solution is added to a sample after sample digestion and analysis. Percent recoveries are calculated for the analyte detected.

3.11 Independent Calibration Verification/ Continuing Calibration Verification (ICV / CCV) – ICV/CCV solutions are made from a stock solution which is different from the stock used to prepare calibration standards and is used to verify the validity of the standardization. This is sometimes referred to by New Jersey as CCS (Calibration Check Standard), or QCS (Quality Control Sample). Method 218.7 calls the ICV a QCS and the CCV a CCC (Continuing Calibration Check).

3.12 Initial Calibration Blank (ICB) - A blank run immediately after calibration to determine if the instrument is adequately zeroed.

3.13 Continuous Calibration Blank (CCB) - A blank run periodically (every 10 samples after the CCV) to ensure the instrument is still zeroed adequately. The CCB may be used for the MB for waters.

3.14 Preparation Batch - Samples digested together as a unit, not to exceed 20 investigative samples. The Digested QC (PB, LCSs, MSs, DUP) are associated with the preparation batch and may be analyzed in separate analytical batches. See ADM-BATCH for further discussion.

3.15 Analytical Batch - Samples analyzed together as a unit, not to exceed 10 injections for 218.7 or 20 injections for 7199 and 218.6. This batch must contain all of the undigested or instrument QC and may not necessarily contain all of the digested QC associated with the samples in the analytical batch. Typically, the preparation batch QC is analyzed prior to the analysis of client samples to verify that the associated samples are valid for use. See ADM-BATCH for further discussion. The analytical sequence for 218.7 is attached.

3.16 Method Detection Limit (MDL): a statistically derived value representing the lowest level of target analyte that may be measured by the instrument with 99% confidence that the value is greater than zero.

3.17 Method Reporting Limit (MRL): The minimum amount of a target analyte that can be measured and reported quantitatively.

3.18 Limit of Detection (LOD): An estimate of the minimum amount of a substance that an analytical process can reliably detect. An LOD is analyte- and matrix- specific and may be laboratory-dependent. For DOD, the smallest amount or concentration of a substance that must be present in a sample in order to be detected at a high level of confidence (99%). At the LOD, the false negative rate (Type II error) is 1%.

3.19 Limit of Quantitation (LOQ)/Reporting Limit: The minimum levels, concentrations, or quantities of a target that can be reported with a specified degree of confidence. For DOD, the lowest concentration that produces a quantitative result within specified limits of precision and bias. The LOQ shall be set at or above the concentration of the lowest calibration standard.

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4.1 All appropriate safety precautions for handling reagents and samples must be taken when performing this procedure. This includes the use of personnel protective equipment, such as, safety glasses, lab coat and the correct gloves.

4.2 Chemicals, reagents and standards must be handled as described in the company safety policies, approved methods and in MSDSs where available. Refer to the Environmental, Health and Safety Manual and the appropriate MSDS prior to beginning this method.


4.4 Waste Management And Pollution Prevention

Hexavalent chromium solutions should be dumped in the red inorganic carboys which will later be emptied by qualified personnel. All other waste can be flushed down the drain with large amounts of water. See SMO-SPLDIS for further information on sample disposal.

It is the laboratory’s practice to minimize the amount of acids and reagent used to perform this method wherever feasible. Standards are prepared in volumes consistent with methodology and only the amount needed for routine laboratory use is kept on site. The threat to the environment from solvent and reagents used in this method can be minimized when recycled or disposed of properly.

The laboratory will comply with all Federal, State and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions as specified in the EH&S Manual.

5) Cautions

• See SOP GEN-300.0 for preventive maintenance of the instrument.

• Clean labware according to GEN-GC. NOTE: Chromic acid must not be used for the cleaning of labware.

6) Interferences

6.1 Contamination - A trace amount of Cr is sometimes found in reagent grade salts. Since a concentrated buffer solution is used in this method to adjust the pH of samples, reagent blanks are analyzed to assess for potential Cr(VI) contamination. Contamination can also come from improperly cleaned glassware or contact or caustic or acidic reagents of samples with stainless steel or pigmented material.

6.2 OXIDATION-REDUCTION (REDOX) CONCERNS – To ensure sample integrity, Cr(VI) must be protected from reduction, and Cr(III), if present, must not oxidize to Cr(VI) during sample storage or processing.

6.2.1 Within the normal pH range in drinking water, Cr(VI), present as a result of pollution or oxidation of Cr(III) in source water during treatment, forms oxyanions, which are typically represented as HCrO4- and CrO42-. The very stable CrO42- anion dominates above pH 8; therefore, the method preservative is designed to buffer samples to at least pH 8. Chromate compounds are quite soluble, mobile and stable, particularly in an oxidizing environment. In contrast, soluble Cr(III) species oxidize to Cr(VI) in the presence of free chlorine, although natural organic matter in surface water sources may

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complex Cr(III), slowing its oxidation even in a highly oxidizing environment. The rate of Cr(III) oxidation increases with chlorine concentration and is pH-dependent. For these reasons, the preservation includes ammonium ions to complex free chlorine. The resulting formation of chloramines minimizes, but does not completely prevent, the oxidation of Cr(III). EPA experiments have demonstrated the ability of the method preservative to minimize the oxidation of Cr(III) and to prevent the reduction of Cr(VI) for at least 14 days in drinking water from ground and surface water sources.

6.2.2 A reducing tendency of the sample matrix may change Cr (VI) to Cr(III). The reducing/oxidizing tendency of each sample may be characterized using additional analytical parameters, such as pH, ferrous iron, sulfides, and oxidation/reduction potential. Other indirect indicators of reducing/oxidizing tendency include Total Organic Carbon (TOC), Chemical Oxygen Demand (COD), and Biochemical Oxygen Demand (BOD). Analysis of these additional parameters establishes the tendency of Cr(VI) to exist in the unspiked sample(s) and may be necessary to assist in the interpretation of QC data for matrix spike recoveries outside conventionally accepted criteria. Reduction of Cr(VI) to Cr(III) can occur in an acidic medium. However, at a pH of 6.5 or greater, CrO42- (which is less reactive than the HCrO4- ) is the predominant species.

6.3 Sample ionic strength may enhance or suppress Cr(VI) response; however, the 4-mm column systems used tolerate typical concentrations of common anions in drinking water in combination with method preservative. Acceptable method performance has been demonstrated by EPA for samples with hardness up to 350 mg/L as CaCO3 and total organic carbon content of 3 mg/L.

6.4 Overloading of the analytical column capacity with high concentrations of anionic species, especially chloride and sulfate, will cause a loss of Cr(VI). The column can handle samples containing up to 5% sodium sulfate or 2% sodium chloride. Poor recoveries from fortified samples and tailing peaks are typical manifestations of column overload.


Personnel must be trained according to CE-QA003.

It is the responsibility of the Project Manager to obtain information from the client before sampling. The laboratory needs to know whether the client will require additional investigation of the sample matrix in the case of matrix spike failures. A reducing condition in the sample matrix will reduce Cr(VI) to Cr(III) causing low bias. Additional parameters – sulfide, pH, REDOX, ferrous irons, BOD, COD, TOC may be used to demonstrate a reducing condition in the sample matrix. If any or all of these parameters are to be analyzed, additional aliquots are to be sampled and the tests are to be scheduled when hexavalent chromium is scheduled due to holding time limitations. If pH and REDOX are to be analyzed, they are to be analyzed from the same DI extract. It is the responsibility of the Project Manager to appropriately flag the data and make notes in the case narrative about the nature of the matrix, if applicable (see the attached flowchart).

It is the responsibility of the analyst to perform the analysis according to this SOP and to complete all documentation required for data review. Analysis and interpretation of the results are performed by personnel in the laboratory who have demonstrated the ability to generate acceptable results utilizing this SOP. Final review and sign-off of the data is performed by the department supervisor or designee.

8) Sample Containers, Collection, Preservations, and Storage

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8.1 Bottleware - If the lab provides the bottleware, waters are sampled in certified clean 250-mL narrow-mouth, high-density polypropylene containers, or equivalent. Soils are sampled in certified clean 4 or 8 oz. glass soil jars. The client must provide additional aliquots of soil sample if further investigation into the reducing/oxidizing nature of the sample is to be done.

8.2 Pretesting – Pre-test each lot of the the preservation solution (buffer). Add 2.5 mL of the buffer to a 250 mL sample bottle and fill with DI. Preservative is acceptable if result is <MDL of the low level analysis.

8.3 Temperature Requirements - Samples are typically shipped and stored at 0-6°C. Drinking water samples for UCMR3 method 218.7 received within 48 hours of collection must be ≤10ºC or they must be rejected. If UCMR3 samples are received after 48 hours of collection they must be ≤6ºC or they must be rejected. The project manager is to notify the client that a new sample must be collected.

8.4 Preservation and Holding Time: Drinking

Water 218.7

Drinking Water 218.6

Non- Potable Water 218.6

Waters 7199

Soil 7199

Air filters NIOSH 7605

Air (impingers) collected by 0061

Filter No Required see 6.4.1

Required see 6.4.1

Optional – Field or Lab

NA NA Field

Preservative NH4OH/ (NH4)2SO4 liquid

NH4OH/ (NH4)2SO4 liquid

NH4OH/ (NH4)2SO4 liquid

None None None None

pH >8.0 9.0-9.5 9.3-9.7 unpreserved NA NA NA Residual Chlorine

<0.1 mg/L NA NA NA NA NA NA

Holding Time 14 days 5 days 28 days 24 hours 7 days from extraction

28 days (recommended)

14 days

Sample pH and residual chlorine (if applicable) is measured and recorded upon receipt (see attached preservation sheet and SMO-GEN for procedures). The preservation sheet and associated steps may be completed by SMO or Wetchem personnel. SMO also records the lot number of the bottle and preservative upon receipt.

• For 218.7, the sample is only valid if received pH>8.0 and Residual chlorine <0.1 mg/L. The sample must be rejected if it does not meet receipt requirements. It may not be reported for UCMR3.

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• For 218.6, the holding times listed only apply if the sample is properly filtered and buffered within 24 hours of sampling. If the buffering requirements (pH) are not met, and the sample is still within 24 hours of collection, the pH is adjusted with the appropriate buffer or ammonium hydroxide.

8.4.1 For 218.6, samples shall be filtered and preserved with buffer solution within 24-hours of collection (preferably in the field at the time of collection). Procedures are as follows, listed in order of preference

8.4.1.1 Filter and Buffer in the Field during time of collection:

Filter sample aliquot using an in-line filter or plastic syringe filtration unit equipped with a 0.45um membrane filter (mfr. Gelman, Millipore, or equivalent).

o Non-Potable Water - Adjust the pH of the filtered sample to pH 9.3 - 9.7 using buffer solution provided by the laboratory. pH meter should be capable of ±0.03 SU. Holding time is 28-days from collection.

o Drinking Water - Adjust the pH of the filtered sample to pH 9.0 - 9.5 using buffer solution provided by the laboratory. pH meter should be capable of ±0.03 SU. Holding time is 5-days from collection.

The bottle set shall include unpreserved 125 or 250 mL plastic bottles. A minimum of 25 mL filtered sample should be provided for analysis.

8.4.1.2 Filter and Buffer in the Field during time of collection –No pH meter available:

Filter sample aliquot using an in-line filter or plastic syringe filtration unit equipped with a 0.45um membrane filter (mfr. Gelman, Millipore, or equivalent). Filtered sample shall be collected in a pre-preserved sample bottle containing buffer solution. Samples must be received by the laboratory within 24-hr of collection to ensure proper pH has been achieved by the buffer solution. The lab will adjust the pH, if necessary, within 24-hr of collection. Holding time is 28-days.

The bottle set shall include pre-preserved 125-ml plastic bottles with 1 mL buffer solution, or equivalent. A minimum of 25 mL filtered sample should be provided for analysis.

8.4.1.3 Filter and Buffer at the Laboratory –No filtration unit or pH meter available:

Collect sample in an un-preserved plastic bottle. Samples must be received by the laboratory within 24-hr for immediate analysis, or in-lab filtration and pH adjustment with buffer solution. Holding time is 28-days for non-potable water and 5 days for drinking water if properly filtered and buffered.

The bottle set shall include unpreserved 125 or 250-mL plastic bottles.

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8.5 Method 7199 water sample: If it is impossible to complete 2 simultaneous injections of all samples within the 24 hour holding time, perform the injections separately in order to meet one injection within holding time of as many samples as possible.

8.6 If investigation is requested, the investigative tests (such as sulfide, pH, REDOX and Fe2+) must be scheduled with the Cr6+ test because some of the investigative test have shorter holding times than hexavalent chromium. These tests must be completed prior to the evaluation of the Cr6+ QC so that the results are available if needed.

8.7 Sample handling, storage, receipt, and custody procedures are discussed in SMO-GEN and SMO-ICOC.



Acquired

Ion Chromatograph Dionex ICS-2100 12030901

Heated Conductivity Cell

DS6 12030664

Reagent Pump AXP 20045075

Variable Wavelength Detector

ICS Series VWD 12031294

Autosampler AS-AP 12031171

Loop 1000 uL

Analytical Column

Dionex AS-7 2x250mm

Computer Workstation Dell Optiplex 790 15105322945

IC #8 (R-IC-08)

Analytical Software Chromeleon 7.0 151838

2012

9.1.1 Reaction Coil: Dionex P/N 042631 750 uL

9.1.2 Column Heater - integrated

9.1.3 Pressurized eluent container, plastic, two liter size.

9.1.4 Nitrogen Tanks

9.2 Labware

9.2.1 Class A volumetric flasks, and graduated cylinders.

9.2.2 Assorted pipettes - of acceptable precision and accuracy – calibrated according to ADM-PCAL.

9.2.3 Disposable syringes - 50-mL, with male luer-lock fittings.

9.2.4 Dionex ONGuard-P sample pretreatment cartridges - p/n 39597

9.2.5 Syringe filters - 0.45-μm, Millipore, p/n SLHV 025 NK.

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9.2.6 Storage bottles - high density polypropylene or amber glass, 1-L capacity.

9.2.7 Orion Model 720A pH meter or Orion SA 520 pH meter, or equivalent, calibrated according to ADM-phSupport, with accuracy ± 0.05 pH.

9.2.8 Analytical and TopLoading Balances – calibrated according to ADM-DALYCK.


10.1 All standards must be traceable using the laboratory lot system (CE-QA007)

10.2 All purchased standards are certified by the vendor. Certificates of Analysis are kept in the department until the standards are no longer being used – at which time they are filed with QA. Certificates of Analysis are available upon request.

10.3 Purchased Reagents and Standards - store at room temperature and expire per Expiration Policy (CE-QA012) unless otherwise indicated.

10.3.1 Ammonium hydroxide, NH4 OH. EM Science cat. #AX1303-14, or equivalent, sp.gr. 0.902, CAS RN 1336-21-6.

10.3.2 Ammonium sulfate, (NH4)2SO4 . EM Science cat #SX0597-1, or equivalent, CAS RN 7783-20-2

10.3.3 1,5-Diphenylcarbazide. EM Science cat. #DX2205-1, or equivalent, CAS RN 140-22-7.

10.3.4 Methanol, HPLC grade, EM Science cat #MX0475-1, or equivalent

10.3.5 Sulfuric acid, concentrated, EM Science, Omnitrace, cat #SX1247-2 or equivalent.

10.3.6 Cr(VI) Standards Stock Solution (1000 mg/L)

10.3.7 Cr(VI) Reference Stock Solution (1000 mg/L) – the Reference Stock is to be from a separate manufacturer of the Standard Stock.

10.3.8 Chlorine Residual Test Strips capable of reading to 0.1 mg/L. HF Scientific Micro Check Test Strips.

10.4 Prepared Reagents

10.4.1 Buffer Solution. Dissolve 3.3 g of ammonium sulfate in 75 mL of reagent water in a 100 mL volumetric flask. Add 6.5 mL of ammonium hydroxide. Dilute to volume (100 mL) with reagent water. Degas the solution with helium gas for 5-10 minutes prior to use. Store at 0-6°C for up to one year.

10.4.2 Buffered DI (Dilution Water). A batch of reagent grade water must be prepared by adjusting the pH within the range of 9-9.5 using the buffer solution. Use this solution for diluting working standards and high level samples. Prepare fresh before use. pH range of 9.3-9.7 shall be used for Method 218.6 waters as per Footnote 20 of EPA Method Update Rule and FAQ-Cr6.

10.4.3 Eluent.- Dissolve 33 g of ammonium sulfate in 500 mL of DI and add 6.5 mL of ammonium hydroxide. Dilute to one liter with reagent water. Degas the solution with helium gas for 5-10 minutes prior to use. Expires 1 month from preparation.

10.4.4 Post-column reagent. Dissolve 0.5 g of 1,5 diphenylcarbazide in 100 mL of HPLC grade methanol in a 1000 mL volumetric flask. In a separate container, add about 500 mL DI, then add 28 mL of 98% sulfuric acid, mix and degas with helium gas for 5-10 minutes. Carefully combine the degassed acid with the

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diphenylcarbazide/methanol solution, introducing as little air as possible. This method of preparation reduces the frequency and intensity of air spikes in the chromatography. Dilute to volume with reagent water. Store in amber glass at 0-6°C. This reagent should be made fresh for the low level analysis, and may be kept no longer than 5 days.

10.5 Standards: 7199/218.6 Regular Level. Prepare fresh before use.

10.5.1 Regular Level Intermediate Standards Working Stock (10 mg/L). Do two 1/10 serial dilutions of the 1000 ppm standard stock solution, using buffered DI.

10.5.2 Initial Calibration Standards: Prepare a series of standards and a blank by pipetting suitable volumes of the Intermediate Standards Working Stock and buffered DI into a dispo cup.

The typical calibration for regular level (7199 and 218.6) is as follows: Standard # Volume (mL) of 10.0 mg/L

Standard Volume buffered DI (mL)

Final Concentration (mg/L)

6 1.00 9.0 1.00 5 0.70 9.3 0.70 4 0.50 9.5 0.50 3 0.10 9.9 0.10 2 1/10 of #3 - 0.01 1 0.0 10 0.000

10.5.3 Regular Level Intermediate Reference Working Stock (10 mg/L) - Do two 1/10 serial dilutions of the 1000 ppm reference stock solution, using buffered DI (as above).

10.5.4 Regular Level ICV/CCV (0.5 mg/L): In a 10mL dispo cup add 9.5 mL buffered DI (as above) and 0.5 mL Intermediate Reference Working Stock.

10.5.5 ICB / CCB / Method Blank / LRB (waters): DI preserved as a sample.

10.5.6 LCS - Regular Level Waters (0.20 mg/L): Add 0.20 mL of 10 mg/L Intermediate Standards Working Stock to 9.8 mL buffered DI. Analyze as a sample.

10.5.7 MS Regular Level Waters (0.2 mg/L): Add 0.20 mL of 10 mg/L Intermediate Standards Working Stock to 10 mL sample.

10.5.8 MB/LCS/MS Soils:prepared and digested according to GEN-3060A.

10.5.9 Post Verification Spike (PVS) – soil extracts only - after digestion, filtration, pH adjustment to 9.0-9.5, and dilution to 100 mLs (as described in GEN-3060), add 0.45 mL of 100 mg/L Cr(VI) standard stock solution to a 45 mL aliquot (this is equal to 40 mg/Kg) OR a concentration twice the original sample, whichever is higher.

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10.6 Standards: 218.7 Prepare fresh before use.

10.6.1 1000 ug/L Standards Working Stock - Add 75 mL of DI to a 100 mL volumetric flask. To this add 1.0 mL Buffer Solution. Add 0.1 mL 1000 mg/L Cr(VI) Standard Stock Solution. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

10.6.2 100 ug/L Standards Working Stock - Add 75 mL of DI to a 100 mL volumetric flask. To this add 1.0 mL Buffer Solution. Add 10 mL 1000 ug/L Cr(VI) Standard Working Stock Solution. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

10.6.3 Initial calibration standards: For each standard, add 75 mL DI to a 100 mL volumetric flask. To this add 1/0 mL Buffer Solution. Then follow the recipe below:

Standard # Volume (mL) of 1000 µg/L Standard

Final Volume with DI (mL)

Final Concentration (µg/L)

8 0.5 100 5.00 7 0.1 100 1.00 6 0.7 mL of 100 ug/L Std 100 0.70 5 0.5 mL of 100 ug/L Std 100 0.50 4 0.3 mL of 100 ug/L Std 100 0.30 3 0.1 mL of 100 ug/L Std 100 0.10 2 10 mL Std#4 100 0.030 1 10 mL Std#3 100 0.010

10.6.4 MS Spiking Stock (10 μg/L). Perform two 1/10 serial dilutions of the 1000 μg/L Standard Stock using DI.

10.6.5 1000 ug/L Reference Working Stock - Add 75 mL of DI to a 100 mL volumetric flask. To this add 1.0 mL Buffer Solution. Add 0.1 mL 1000 mg/L Cr(VI) Reference Stock Solution. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

10.6.6 ICV/CCVs:

10.6.6.1 Low Level (LL-CCV): 0.03 ug/L –

o 100 ug/L Reference Working Stock - Add 75 mL of DI to a 100 mL volumetric flask. To this add 1.0 mL Buffer Solution. Add 10 mL 1000 ug/L Reference Stock Solution. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

o 0.30 ug/L Reference Working Stock - To a 100 mL volumetric flask add about 75 mL DI. To this add 1.0 mL Buffer Solution and 0.3 mL of the 100 ug/L Reference stock. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

o To a separate 100 mL volumetric flask, add about 75 mL DI. To this add 1.0 mL Buffer Solution and 10 mL of the 0.30 ug/L Reference Working Stock. Bring to volume with DI. Prepare fresh before use. Mix thoroughly.

10.6.6.2 Mid Level CCV (ML-CCV) / ICV: 2.5 ug/L – To a 100 mL volumetric flask, add about 50 mL DI. To this add 1.0 mL Buffer Solution and 0.25 mL of 1000 ug/L Reference stock. Bring to volume with DI and mix. Prepare fresh before use.

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10.6.6.3 High Level CCV (HL-CCV): 4.0 ug/L - to a 100 mL volumetric flask, add about 50 mL DI. To this add 1.0 mL Buffer Solution and 0.4 mL of 1000 ug/L Reference. Bring to volume with DI and mix. Prepare fresh before use.

10.6.7 ICB / CCB / Method Blank / LRB (waters): In a 250 mL volumetric flask, add 2.5 mL liquid preservative to about 100 mL DI. Bring to volume with DI and transfer to a 250 mL HDPE sample bottle, received from SMO.

10.6.8 MS/LFSM - Add 0.20 mL of 10 μg/L Low Level LCS/MS Spiking Stock to 10 mL pH adjusted sample.

10.7 Standards: 218.6 Low Level –prepare fresh before use

10.7.1 1000 ug/L Standards Working and Reference Stocks – same as 218.7.

10.7.2 100 ug/L Standard Working Stock – make a 1/10 dilution of the 1000 ug/L Standard Working stock.

10.7.3 ICAL standards – Standard # Volume (mL) of 1000 µg/L

Standard Final Volume with buffered DI (mL)

Final Concentration (µg/L)

6 0.1 100 1.00 5 0.7 mL of 100 ug/L Std 100 0.70 4 0.5 mL of 100 ug/L Std 100 0.50 3 0.2 mL of 100 ug/L Std 100 0.20 2 10 mL of Std#6 100 0.10 1 10 mL Std#3 100 0.020 0 0 100 0

10.7.4 LCS/MS Spiking Stock (10 μg/L). Perform two 1/10 serial dilutions of the 1000 μg/L Standard Stock.

10.7.5 ICV/CCV (0.5 μg/L): To 5 mL buffered DI (as above) add 5 mL 1.0 μg/L Low Level Intermediate Reference Working Stock.

10.7.6 LCS (0.20 μg/L): Add 0.20 mL of 10 μg/L Low Level LCS/MS Spiking Stock to 9.8 mL buffered DI. Analyze as a sample.

10.7.7 Matrix Spike(0.20 μg/L): Add 0.20 mL of 10 μg/L Low Level LCS/MS Spiking Stock to 10 mL pH adjusted sample.

10.7.8 ICB/CCB/MB – same as 218.7

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11.1 Follow policies in ADM-ICAL unless otherwise specified in this SOP.

11.2 Initial Calibration

11.2.1 For New Jersey - Inject a calibration blank. Be sure this calibration blank is less than the MDL before continuing.

11.2.2 Number of Standards - Calibrate the instrument using the standards prepared as per the Standards and Reagents Section. Six or more standards must be used for 218.7. Three or more standards must be used for 218.6. A blank and three or more standards must be used for 7199. If a quadratic fit is to be used, analyze at least 6 standard levels plus blank.

11.2.3 Frequency – Initially and whenever continuing calibration verification criteria cannot be met.

11.2.4 Calibration Fit– Construct a calibration curve of analyte response (peak area) versus analyte concentration. The curve may be first order (y=mx+b), or second order (quadratic). Weighting may be used (1/x).

11.2.5 Limits –

11.2.5.1 For first order polynomial, the coefficient of correlation must be 0.999 or greater. File the printout of the linear regression with the ICAL.

11.2.5.2 For second order, mark the linear regression printout so that it is clear that the linear was for verification only. The accuracy of the quadratic calibration is verified by assessing the recovery of each standard. The recovery of each standard above the LOQ must be within 10% for 218.6 and 7199.

11.2.5.3 The LOQ standard must be within ±50% of the true value.

11.2.5.4 For 218.7, all standards above the LOQ must be within ±15% of the true value (regardless of curve type).

11.2.6 ICV(QCS) - Analyze an ICV immediately after the calibration standards. The ICV must be within limits to use the curve. The limits are 90-110% for 7199, 95-105% for 218.6, and 85-115% for 218.7. If the correctly prepared ICV is not compliant, the second source standard does not verify the curve. Fix the problem and recalibrate. If the ICV was prepared incorrectly, the curve may be used if a correctly prepared ICV verifies the curve.

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11.3 Continuing Calibration Verification and Blank

11.3.1 Frequency - run a CCV and CCB set to start a daily run, every ten injections (or 24 hours, whichever is more frequent), and at the close of the run. For water samples, one blank counts as both the CCB and the MB. For 218.7, the CCV concentration varies (see attached Analytical Sequence and Standards and Reagents Section).

11.3.2 Limits –

11.3.3 CCV Corrective Action - If a CCV fails, corrective actions must be performed. If routine corrective action fails to produce a second consecutive (immediate) acceptable CCV, then either the lab has to demonstrate acceptable performance after corrective action with two consecutive CCVs or a new ICAL must be performed.

11.3.4 Blank Corrective Action - Sample results greater than 10 times the result of the contaminated blank may be reported without qualification. Samples <10x blank contamination must be reanalyzed with a compliant blank whenever possible. If samples associated with a contaminated blank are not repeated (due to holding time restrictions, etc.), the data must be qualified on the report.


12.1 Sample preparation.

12.1.1 Waters - Allow pH-adjusted samples to equilibrate to ambient temperature prior to analysis. Samples that have not been pH adjusted should be adjusted to pH 9-9.5 by dropwise addition of buffer solution. Record the pH adjustment and the pH meter ID on the benchsheet. If salts are formed as a result of the pH adjustment, the filtrate must be filtered again prior to analysis. pH range for 218.6 non-potable waters shall be 9.3-9.7 due to footnote 20 of EPA method update rule and FAQ-Cr6. All drinking waters are to be pH 9.0-9.5.

12.1.2 Soils – Digest according to GEN-3060A except pH adjust the sample to 9.0-9.5 instead of 7.5±0.5.

12.1.3 Air Filters – Prepare according to GEN-7605.

Method ICB/CCB/MB Limit

7199 7605 <MRL 7199 NJ <MDL 218.6 <LOD 218.7 <0.01 ug/L NIOSH 7605 <MRL

Method CCV % Recovery

7199 90-110 218.6 95-105 218.7 85-115 NIOSH 7605 85-115

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12.2 Establish Operating Conditions: IC #5 IC #8 Warm up 45-60 minutes 45-60 minutes Eluent flow rate 1.0 mL/min 0.36 mL/min Post-column flow rate ~0.33 mL/min ~0.12 mL/min Column heater 30ºC 30ºC Sample loop 2000 uL (LL) or 100 uL (RL) 1000 uL Wavelength 530 nm 530 nm

Check flow rate of waste after the flow cell prior to calibration and sample analysis.

12.3 Sample Analysis.

12.3.1 Standards and samples are injected onto the column using an autosampler.

12.3.2 Color Interference - The guard column should be removing any inherent color in samples. If, however, a sample appears colored after elution through the columns, it is possible that not all sample color/organic material was removed and a false positive due to color could occur. At this point, pass a sample aliquot through Dionex ONGuard-P syringe filters and re-analyze. Alternatively, re-analyze a sample aliquot, but replace the post-column reagent with the matrix match reagent and subtract the matrix-match reagent result from the post-column reagent result.

12.3.3 Double Injection – 7199 requires that samples are injected twice (double injections are not required for 218.6 nor 218.7). The RPD between the samples must be less than 20 if the sample concentration is ≥ four times the reporting limit. A control limit of ± the reporting limit is used when the sample concentration is < four times the reporting limit. If it is impossible to meet holding times for both injections, it is best to inject samples once within holding time and make the second injection out of holding time. Report both results. Label the comments field R1, R2, R3, R4, etc.

12.4 Sample Evaluation –

12.4.1 Each chromatogram is reviewed for compliance and initialed by the reviewer. All chromatographic baselines should be examined by a knowledgeable analyst to ensure that proper integrations have been made by the analytical software. Especially for the low level analysis, care must be taken to ensure proper identification and integration of all low level peaks approaching a signal to noise ration of 3:1. When the data system incorrectly quantitates or identifies analytes, manual integration is necessary. Data must be integrated consistently between standards, samples, and QC. See CE-QA002 for integration requirements and manual integration documentation.

12.4.2 Samples or extracts exceeding the highest calibration standard (including PVS) must be diluted using buffered DI and re-analyzed.

12.4.3 Sample must be bound by acceptable analytical QC and from a batch with acceptable batch QC. Double injection must meets limits.

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13) Troubleshooting

13.1 See Instrument manual or maintenance log for help with solving specific analytical or instrument problems.

13.2 Maintenance log - All Preventive maintenance, as well as instrument repair, should be documented in the appropriate instrument maintenance log. Most routine maintenance and troubleshooting are performed by laboratory staff. Other maintenance or repairs may, or may not require factory service, depending upon the nature of the task. Any maintenance performed by outside services must also be documented – either through notes in the log or through documents provided by the service. The log entries will include the date maintenance was performed, symptoms of the problem, serial numbers of major equipment upgrades or replacements. The datafile name of the first acceptable run after maintenance is to be documented in the maintenance log.


Data is uploaded electronically from the instrument to LIMS. As applicable, sample volumes, weights, and dilutions are entered to LIMS and final results are adjusted by LIMS accordingly. Calculations are presented in the following section.

15) Calculation and Data Reduction Requirements

15.1 Determine the concentration of the injected sample from the calibration curve.

15.1.1 For waters, multiply the injected concentration by dilution (use 1 if there is no dilution). Report in mg/L except report in μg/L for low level 218.6 and 218.7.

15.1.2 For digested soils: Concentration (mg/Kg dry wt.) = A x D x E B x C where: A = Concentration observed in the digest (mg/L) B = Initial moist sample weight (g) C = % Solids/100 D = Dilution factor E = Final digest volume (mL)

15.1.3 For air stips (NIOSH 7605) – see GEN-N7605.

15.2 Report both of the results from the double injection (if applicable).

15.3 For NJ - Data is “R” flagged if the MS is outside of 50-150%, if CCV or LCS is out of control, if calibration CC<0.999, if calibration blank >MDL, if PB >MDL for samples >MDL, if a water sample is run beyond 48 hours from sampling, if required QC is not performed, or if a soil sample is not redigested as required.

15.4 For NJ - Data is “J” flagged if the result is run between 24 and 48 hours from sampling (waters only), if QC is not performed at the correct frequency, if the MS is outside of limits but within 50-150%, if the RPD of a double injection or a DUP is greater than 20, if digested QC fails the initial and the redigestion, or if PDS <85%.

15.5 If samples are redigested, report as replicates. Both original and redigested data is reported.

15.6 All sample data and QC data, including calibration verification must reference the name

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(date or filename) of the ICAL on the raw data report. The current system lists the ICAL under the heading of “Quantif. Method” and the convention is to use the IC# and date in the name. For Example: “5-121610” is IC#5 on 12/16/10.

15.7 Data must be reviewed by the analyst and a peer (supervisor or qualified analyst) using a Data Quality Checklist before the results are validated and reported to the client. Further data review policies and procedures are discussed in ADM-DREV.

16) Quality Control, Acceptance Limits and Corrective Action

16.1 ICV/CCV and ICB/CCB/MB requirements are in the Calibration Section.

16.2 For Water Samples

16.2.1 Matrix Spike –

16.2.1.1 Frequency - A minimum of one matrix spike sample per sample batch (1/10 for 218.6) must be analyzed to check for matrix interference.

16.2.1.2 Limits - The recovery of the matrix spike must be within limits in the Data Quality Objectives Table. For 218.7 – the MS must be within 15%.

Method MS Limit 7199 DQO Table 7199 NJ DQO Table 218.6 90-110 218.7 85-115

16.2.1.3 Corrective Action - If the matrix spike recovery fails these limits, report with appropriate qualifiers.

16.2.2 DUP/MSD

16.2.2.1 Frequency - A minimum of one duplicate sample per sample batch must be analyzed to check for precision. Alternatively, a Matrix Spike Duplicate may be used instead of a Duplicate. The MSD is required for UCMR3.

16.2.2.2 Limits: RPD Other 7199 <20 +/-MRL if <4xMRL 218.6 <20 +/-MRL if <4xMRL 218.7 <15 NA

16.2.2.3 Corrective Action - If the RPD is out of limits, repeat the sample and duplicate unless there is assignable matrix interference, historical failures, or lack of volume. If an out of control duplicate is not repeated, note the reason on the data quality checklist. If, at the time when the problem is discovered, the sample exceeds twice the holding time, discuss with supervisor or Project Manager prior to repeating the samples. Report all of the replicates and explain in the checklist for the case narrative.

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16.2.3 LCS -

16.2.3.1 Frequency –An LCS must be analyzed with every batch for 7199 and 218.6. An LCS is not required for 218.7 (performance measured with CCV). See GEN-N7605 for air strips.

16.2.3.2 Limits – Method Limits 7199 DQO Table 218.6 90-110% 218.7 NA

16.2.3.3 Corrective Action - If the LCS fails these limits, correct the problem and reanalyze the affected samples or flag the associated data.

16.3 For Samples Digested by GEN-3060A – see also the attached flowchart. Undigested QC (LCS, MB, DUP, MS) is not required to be analyzed with the digested QC in a 7199 run which only has digested samples.

16.3.1 MB - A preparation blank must be prepared and analyzed with each digestion batch. Detected Cr(VI) concentrations must be less than the reporting limit (less than the MDL for New Jersey) or the batch must be redigested and reanalyzed. If the samples are out of holding time, redigest and reanalyze and both sets of data will be reported. If insufficient sample volume necessitate the use the data, flag the data associated with the non-compliant PB (the entire preparation batch – not just those in the analytical batch).

16.3.2 LCS Insoluble – An insoluble LCS must be prepared and analyzed with each digestion batch. Recovery must be within 80-120% or the entire sample batch must be redigested and reanalyzed. If the samples are out of holding time, redigest and reanalyze and both sets of data will be reported. If insufficient sample volume necessitate the use the data, flag the data associated with the non-compliant LCS (the entire preparation batch – not just those in the analytical batch)

16.3.3 DUP - A separately prepared duplicate soil sample must be analyzed at a frequency of one per batch. Duplicate samples must have a Relative Percent Difference (RPD) of ≤ 20%, if the sample concentration is ≥ four times the reporting limit. A control limit of ± the reporting limit is used when the sample concentration is < four times the reporting limit. If the RPD of the duplicates is out of limits, repeat the sample and duplicate unless there is assignable matrix interference, historical failures, or lack of volume. If an out of control duplicate is not repeated, note the reason on the data quality checklist. If, at the time when the problem is discovered, the sample exceeds twice the holding time, discuss with supervisor or Project Manager prior to repeating the samples. Report all of the replicates and explain in the checklist for the case narrative.

16.3.4 MS- Both soluble an insoluble digested matrix spikes must be analyzed at a frequency of one each per batch. Both matrix spike recoveries must be within 75-125% of the true value. If either of the matrix spike recoveries are not within these recovery limits the entire batch must be redigested and reanalyzed. If the reanalysis also fails the 75-125% limit, sample data is flagged. Exception – if the sample concentration is greater than 4 times the spike concentration, the spike is “diluted out” and is not used to evaluate the batch (redigestion is not required). The client should be notified of the possible condition of the sample and further investigation is needed using the oxidation/reduction parameters discussed in 4.1. If the samples are out of

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holding time for the reanalysis, redigest and reanalyze and both sets of data will be reported. If insufficient sample volume necessitate the use the data, flag the data associated with the non-compliant LCS (the entire preparation batch – not just those in the analytical batch).

16.3.5 A post-digestion Cr(VI) matrix spike must be analyzed per batch, whether or not the MS passed or failed. Use the attached PVS Calculation sheet. The criteria for the post digestion matrix spike recovery is 85-115% recovery. If spike recovery is outside limits, and the matrix spike also failed, no further action is needed apart from the corrective action for the MS. The corrective actions will show whether these digestates may contain soluble reducing agents for Cr(VI). If the PVS fails and the MS passes, reanalyze the PVS.


See CE-GEN003 and ADM-ARCH

18) Contingencies for Handling Out of Control Data

If data is produced that is out of control and is not to be re-analyzed due to sample volume restrictions, holding times, or QC controls can not be met, data is flagged with the appropriate data qualifiers.


19.1 Reporting limits are based upon an MDL study performed according to CE-QA011 and filed in the MDL binders in the QA office.

19.2 Demonstration of Capability is performed according to CE-QA003.

19.3 From the EPA Method 7199:

• Single Laboratory Precision and Accuracy is available in Table 3

• Single Analyst Precision, overall precision and Recovery from Multilaboratory Study is available in Table 4.


• Added NIOSH 7605 throughout.

• Removed IC-5

• Updated to current ALS format.


• Test Methods for Evaluating Solid Waste Physical/Chemical Methods, USEPA SW-846.

• NJDEP Standard Operating Procedure (SOP No.5.A.10) Dated August 15, 2005: Standard Operating Procedure for Analytical Data Validation of Hexavalent Chromium.

• Methods for the Determination of Metals in Environmental Samples, Supplement I. EPA/600/R-94/111. May 1994. Method 218.6 revision 3.3.

• Method 218.7: Determination of Hexavalent Chromium in Drinking Water by Ion Chromatography with Post-Column Derivatization and UV-Visible Spectroscopic Detection. EPA Document Number EPA 815-R-11-005. Version 1.0, November 2011.

• NIOSH Manual of Analytical Methods, Fourth Edition, Method 7605 Issue 1, March 15, 2003.

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22) Attachments

• Table 3 Single Laboratory Precision and Accuracy

• QC Flowchart

• PVS Calculation Sheet

• PH Adjustment Sheet – controlled separately on the Controlled Forms section of the Rochester Intranet.

• eH/pH diagram

• Analytical Sequence

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Analytical Sequence for Method 218.7 Injection Number Sample ID Injection Number Sample ID

1 Calibration Standard 1 22 Analytical Sample 9 2 Calibration Standard 2 23 Analytical Sample 10 3 Calibration Standard 3 24 Analytical Sample 11 4 Calibration Standard 4 25 Analytical Sample 12 5 Calibration Standard 5 26 Analytical Sample 13 6 Calibration Standard 6 27 Analytical Sample 14 7 Calibration Standard 7 28 Analytical Sample 15 8 LL-CCV 29 Analytical Sample 16 9 CCB 30 Analytical Sample 16 Spike

10 Analytical Sample 1 31 Analytical Sample 16 Spike Dup 11 Analytical Sample 2 32 HL-CCV 12 Analytical Sample 3 33 CCB 13 Analytical Sample 4 34 Analytical Sample 17 14 Analytical Sample 5 35 Analytical Sample 18 15 Analytical Sample 6 36 Analytical Sample 19 16 Analytical Sample 7 37 Analytical Sample 20 17 Analytical Sample 8 38 Analytical Sample 20 Spike 18 Analytical Sample 8 Spike 39 Analytical Sample 20 Spike Dup 19 Analytical Sample 8 Spike Dup 40 ML-CCV 20 ML-CCV 41 CCB 21 CCB

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DOCUMENT TITLE: ALKALINE DIGESTION FOR HEXAVALENT CHROMIUM IN SOIL

REFERENCED METHOD: SW846 3060A

SOP ID: GEN-3060

REV. NUMBER: 3


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Cr6+ Soil Digest GEN-3060 Rev: 3 Effective: 3/1/2013 Page i of i

ALS GROUP USA, CORP. Part of the ALS Group An ALS Limited Company


TABLE OF CONTENTS 1) Scope and Applicability...................................................................................................................................1 2) Summary of Procedure ...................................................................................................................................1 3) Definitions.........................................................................................................................................................1 4) Responsibilities.................................................................................................................................................2 5) Interferences.....................................................................................................................................................2 6) Safety ................................................................................................................................................................3 7) Sample Collection, Containers, Preservation, and Storage..........................................................................3 8) Apparatus and Equipment..............................................................................................................................4 9) Standards, Reagents, and Consumable Materials ........................................................................................5 10) Preventive Maintenance..................................................................................................................................7 11) Procedure .........................................................................................................................................................7 12) Quality Assurance/Quality Control Requirements.......................................................................................9 13) Data Reduction and Reporting.....................................................................................................................10 14) Method Performance.....................................................................................................................................10 15) Waste Management and Pollution Prevention............................................................................................10 16) Corrective Action for Out-of-Control Data.................................................................................................10 17) Contingencies for Handling Out-of-Control or Unacceptable Data..........................................................10 18) Training ..........................................................................................................................................................11 19) Method Modifications ...................................................................................................................................11 20) Summary of Changes ....................................................................................................................................11 21) References.......................................................................................................................................................11 22) Attachments ...................................................................................................................................................11

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Cr6+ Soil Digest GEN-3060 Rev. 3 Effective: 3/1/2013 Page 1 of 15




1.1 This SOP uses USEPA Method 3060A for extracting hexavalent chromium [Cr(VI)] from soluble, adsorbed, and precipitated forms of chromium compounds in soil, sludge, sediment, and some industrial waste materials. To quantify total Cr(VI) in a solid matrix, three criteria must be satisfied: (1) the extracting solution must solubilize all forms of Cr(VI), (2) the conditions of the extraction must not induce reduction of native Cr(VI) to Cr(III), and (3) the method must not cause oxidation of native Cr(III) contained in the sample to Cr(VI).

1.2 The quantification of Cr(VI) in the digestates produced by this SOP is performed using Method 7196A (See GEN-7196A) or Method 7199 (see GEN-7199).

1.3 The reporting limits are listed in the analytical SOPs.


2.1 This procedure is an alkaline digestion to solubilize Cr(VI) compounds in solid samples. The pH of the digestate must be carefully adjusted during the digestion procedure. Failure to meet the pH specifications will necessitate redigestion of the samples. The sample is digested using a Na2CO3/NaOH solution and heated to dissolve the Cr(VI) and stabilize it against reduction to Cr(III).

2.2 Analysis of Cr(VI) solubilized in the alkaline digestate is accomplished by reaction with diphenylcarbohydrazide (Method 7196A or 7199). It is highly selective for Cr(VI), and few interferences are encountered when it is used on alkaline digestates.

3) Definitions

3.1 Soluble Matrix Spike (MS-Sol) - In the soluble matrix spike analysis, a predetermined quantity of a soluble standard solution of the analyte is added to a sample matrix prior to sample digestion and analysis. The purpose of the soluble matrix spike is to evaluate the effects of the sample matrix on the methods used for the analyses. Percent recovery is calculated for the analyte detected.

3.2 Insoluble Matrix Spike (MS-Insol) - In the insoluble matrix spike analysis, a predetermined quantity of an insoluble standard of the analyte is added to a sample matrix prior to sample digestion and analysis. The purpose of the insoluble matrix spike is to evaluate the dissolution during the digestion process and effects of the sample matrix on the dissolution. Percent recovery is calculated for the analyte detected.

3.3 Duplicate Sample (DUP) - A laboratory duplicate. The duplicate sample is a separate field sample aliquot that is processed in an identical manner as the sample proper. The relative percent difference between the samples is calculated and used to assess analytical precision.

3.4 Method Blank (MB) - The method blank is an artificial sample designed to monitor introduction of artifacts into the process. The method blank is carried through the entire analytical procedure.

3.5 Insoluble Laboratory Control Sample (LCS-Insol) – In the LCS-Insol analysis, a predetermined quantity of an insoluble standard solution is added to a blank prior to sample digestion and analysis. Percent recovery is calculated for the analyte detected.

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3.6 Post Verification Spike (PVS) – A predetermined quantity of standard solution is added to a sample matrix after digestion and after the sample is pH adjusted and brought up to 100 mLs. Percent recoveries are calculated for the analyte added. This is described in the analytical procedures.

3.7 Preparation Batch - Samples digested together as a unit, not to exceed 20 samples. The Digested QC samples are associated with the preparation batch and may be analyzed in separate analytical batches. See ADM-BATCH for further discussion.

4) Responsibilities

4.1 It is the responsibility of the Project Manager to obtain information from the client before sampling. The laboratory needs to know whether the client will require additional investigation of the sample matrix in the case of matrix spike failures. A reducing condition in the sample matrix will reduce Cr(VI) to Cr(III) causing low bias. Additional parameters – sulfide, pH, REDOX, ferrous irons, BOD, COD, TOC may be used to demonstrate a reducing condition in the sample matrix. If any or all of these parameters are to be analyzed, additional aliquots are to be sampled and the tests are to be scheduled when hexavalent chromium is scheduled due to holding time limitations. It is the responsibility of the Project Manager to appropriately flag the data and make notes in the case narrative about the nature of the matrix, if applicable (see the attached flowchart).

4.2 It is the responsibility of the analyst to perform the analysis according to this SOP and to complete all documentation required for data review. Analysis and interpretation of the results are performed by personnel in the laboratory who have demonstrated the ability to generate acceptable results utilizing this SOP. Final review and sign-off of the data is performed by the department supervisor or designee.

5) Interferences

5.1 A reducing tendency of the sample matrix may change Cr (VI) to Cr(III). The reducing/oxidizing tendency of each sample may be characterized using additional analytical parameters, such as pH, ferrous iron, sulfides, and oxidation/reduction potential. Other indirect indicators of reducing/oxidizing tendency include Total Organic Carbon (TOC), Chemical Oxygen Demand (COD), and Biochemical Oxygen Demand (BOD). Analysis of these additional parameters establishes the tendency of Cr(VI) to exist in the unspiked sample(s) and may be necessary to assist in the interpretation of QC data for matrix spike recoveries outside conventionally accepted criteria.

5.2 Substances not typically found in the alkaline digests of soils may interfere in the analytical techniques for Cr(VI) following alkaline extraction if the concentration of these interferences are high relative to the Cr(VI) concentration. Refer to EPA methods 7196A and 7199 for a discussion of the specific agents that interfere with Cr(VI) quantification.

5.3 For materials suspected of containing high concentrations (greater than four times the laboratory Cr(VI) reporting limit) of soluble Cr(III), Cr(VI) results obtained using Method 3060A may be biased high due to method induced oxidation. The addition of Mg2+, and a phosphate buffer, to the alkaline extraction solution has been shown to suppress oxidation.

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5.4 One of the most insoluble forms of chromate in alkaline solution, barium chromate, may require additional heating time to affect complete dissolution in some soil matrices.

5.5 Reduction of Cr(VI) to Cr(III) can occur in an acidic medium. However, at a pH of 6.5 or greater, CrO42- (which is less reactive than the HCrO4- ) is the predominant species.

6) Safety

• All appropriate safety precautions for handling solvents, reagents and samples must be taken when performing this procedure. This includes the use of personnel protective equipment, such as, safety glasses, lab coat and the correct gloves.

• Chemicals, reagents and standards must be handled as described in the company safety policies, approved methods and in MSDSs where available. Refer to the Environmental, Health and Safety Manual and the appropriate MSDS prior to beginning this method.

• Sodium Hydroxide (NaOH) is a strong caustic and a severe health and contact hazard. Use nitrile or latex gloves while handling pellets or preparing solutions.

• Nitric and sulfuric acids are used in this method. These acids are extremely corrosive and care must be taken while handling them. A face shield should be used while pouring acids. And safety glasses should be worn while working with the solutions. Lab coat and gloves should always be worn while working with these solutions.

• Refer to the Safety Manual for further discussion of general safety procedures and information.

7) Sample Collection, Containers, Preservation, and Storage

7.1 Samples should be collected using devices that do not contain stainless steel. Sample containers provide by the lab are purchased, pre-cleaned, certified 8 oz. wide mouth clear glass jars with Teflon lined lids. The client must provide additional aliquots of sample if further investigation into the reducing/oxidizing nature of the sample is to be done.

7.2 Samples should be stored at 0-6°C until analysis.

7.3 If investigation is requested, the investigative tests (such as sulfide, pH, REDOX and Fe2+) must be scheduled with the Cr6+ test because some of the investigative test have shorter holding times than hexavalent chromium. These tests must be completed prior to the evaluation of the Cr6+ QC so that the results are available if needed.

7.4 Holding Times

7.4.1 Samples may be held for 30 days from collection to digestion.

7.4.2 7199: Once the samples have been digested, they may be held overnight in tightly capped B-cups in the cooler at 0-6 °C. Holding the samples overnight facilitates settling and subsequent filtering. Samples must be filtered, pH adjusted, and analyzed within 7 days of digestion.

7.4.3 7196A - Once the extracts are pH adjusted to 7.5 ± 0.5, samples are required to be analyzed within 1-hour. Samples must be filtered, pH adjusted, and analyzed within 7 days of digestion.

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7.5 For further sample handling, storage and custody procedures, see SMO-GEN and SMO-ICOC.

8) Apparatus and Equipment

8.1 Glassware: Beakers (150 mL), watch glass covers, graduated cylinders (50 mL), volumetric flasks (Class A, 1000 mL), rinsed with 50/50 Nitric Acid.

8.2 Filtration apparatus and filter membranes (0.45, μm), preferably cellulosic or polycarbonate membranes.

8.3 Hot block – Environmental Express SC154 (SN7021CECW3005) – with Stirbase and controller. Capable of maintaining the digesting samples at 90-95°C, and Teflon coated stir bars. The temperature of the sample is monitored as described in the procedure. This is the primary equipment used.

8.4 Stirring hot plates, capable of maintaining the digesting samples at 90-95°C, and Teflon coated stir bars. The hot plates currently in use are all single - place stirring. Plates are to be studied and the position marked on the temperature control dial where the dial should be adjusted to maintain 90-95 °C. The temperature of the sample is monitored as described in the procedure. The manufacturers of the hot plates are VWR, Thermolyne and Corning.

8.5 pH meter: Orion Model 720A and/or Orion Model SA520 with Thermo-Orion combination pH electrodes. Meters are to be calibrated and used according to ADM-pHSupport.

8.6 Balances: Top-Loading – American Scientific products Model DTL 2500g; Analytical – Mettler AE240. Calibrated according to ADM-DALYCK.

8.7 Thermometers – calibrated according to ADM-DALYCK.

8.8 B-cups - 130 mL plastic beakers.

8.9 Micropipettes – Eppendorf 100-1000 uL and 10-100 uL. Calibrated according to ADM-PCAL. IDs of pipettes used during analysis are documented on the digestion and analysis benchsheets so that pipettes can be traced back to pipette calibration logs.

8.10 Computer Hardware and Software – Any computer in the lab which is connected to the LAN and has access to the LIMS and the Excel benchsheet.

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9) Standards, Reagents, and Consumable Materials

9.1 All Standards must be traceable using the laboratory lot system (CE-QA007). All purchased standards are certified by the vendor. Certificates of Analysis are kept in the department until the standards are no longer being used – at which time they are filed with QA. Certificates of Analysis are available upon request. Purchased standards are routinely checked against an independent source for analyte concentration.

9.2 Purchased Reagents and Standards – Store at room temperature and expire per the Expiration Policy unless otherwise indicated.

9.2.1 Nitric acid: HNO3, concentrated, analytical reagent grade or spectrograde quality. Store in the dark. Expires sooner than assigned date if the solution develops a yellow color.

9.2.2 Sodium carbonate: Na2CO3, anhydrous, analytical reagent grade.

9.2.3 Sodium hydroxide pellets: NaOH, analytical reagent grade.

9.2.4 Magnesium Chloride: MgCl2 (anhydrous), analytical reagent grade. 392.18 mg MgCl2 is equivalent to 100 mg Mg2+.

9.2.5 K2HPO4: Analytical reagent grade.

9.2.6 KH2HPO4: analytical reagent grade.

9.2.7 Sulfuric acid (H2SO4), concentrated, reagent grade.

9.2.8 Cr (VI) standard solution (1000 mg/L): purchased commercially - certified primary standard solution.

9.2.9 Cr (VI) reference solution (1000 mg/L): purchased commercially - certified primary standard solution from a separate source as the standard solution.

9.2.10 Lead Chromate, (PbCrO4), powder

9.3 Prepared Reagents – Store at 0-6 °C and expire per the Expiration Policy unless otherwise indicated.

9.3.1 Phosphate Buffer - 0.5M K2HPO4/0.5M KH2PO4 buffer at pH 7 (also called 1M Phosphate buffer): Dissolve 87.09 g K2HPO4 and 68.04 g KH2PO4 into 700 mL of DI. Transfer to a 1L volumetric flask and dilute to volume.

9.3.2 Digestion solution: Dissolve 20.0 ± 0.05 g NaOH pellets and 30.0 ± 0.05 g Na2CO3 in DI in a one-liter volumetric flask and dilute to the mark. Store the solution in a tightly capped polyethylene bottle. The pH of the digestion solution must be checked before using. Expires in 1 month or if the pH is not 11.5 or greater.

9.3.3 10% Sulfuric acid (v/v) (1.8M): Add 10 mL of concentrated H2SO4 to approximately 70 mL of DI. Mix well and let cool. Dilute to a final volume of 100 mL with DI.

9.3.4 50/50 Nitric acid wash solution: Slowly and carefully combine 1 part concentrated Nitric Acid with 1 part DI.

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9.4 Prepared Standards – Prepare fresh daily.

9.4.1 Cr (VI) intermediate standard solution (100 mg/L): dilute 1.00 mL of 1000 mg/L standard solution to 10.0 mL with DI.

9.4.2 Cr (VI) intermediate reference solution (100 mg/L): dilute 1.00 mL of 1000 mg/L reference solution to 10.0 mL with DI.

9.4.3 Calibration Standards for 7196A: Vol. 100 mg/L Volume of Final Conc. (mg/L) stock (mLs) digest solution Volume (mL) 2.0 2.00 50 100 1.5 1.50 50 100 1.0 1.00 50 100 0.5 0.50 50 100 0.1 0.10 50 100 0.0 0.00 50 100 7196A standards are adjusted to a pH of 7.5 +/- 0.5 with concentrated nitric acid before they are brought to a final volume of 100 mLs with DI. Must be analyzed within 1 hour after pH adjustment.

9.4.4 Calibration Standards for 7199 – as described in the 7199 SOP. These standards do not undergo these procedures. They are made with buffered DI (pH 9.0-9.5).

9.4.5 ICV/CCV for 7196A (1.0 mg/L): add 1.0 mL 100 mg/L reference solution to 50 mL digest solution. Adjust pH to 7.0 - 8.0 with concentrated nitric acid. Bring to 100 mL with DI. Must be analyzed within 1 hour after pH adjustment.

9.4.6 ICV/CCV for 7199- as described in the 7199 SOP. This standard does not undergo these procedures. It is made with buffered DI (pH 9.0-9.5).

9.5 Soluble MS (1.0 mg/L or 40 mg/Kg): add 1.0 mL 100 mg/L standard solution to sample or blank (Ottawa sand) and 50 mL digest solution. Sample is digested, filtered, and completed as a sample including pH and volume adjustment.

9.6 Insoluble LCS – Add approximately 10 mg PbCrO4 to 50 mLs digest solution. Digest and analyze as a sample. The true value will depend on the amount used. Lead chromate is 0.161% chrome. The 0.0025 is as if it was spiked into 2.5 g sample weight.

%161.00025.0

)/( 4×=

mgPbCrOkgmgTrueValue

9.7 Insoluble MS - Add 10 mg PbCrO4 to sample. Digest and analyze. Calculate true value

as above.

9.8 PVS – described in the analytical SOPs since it is not done during digestion.

9.9 Method Blank – Analyze Ottawa Sand as a sample.

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10) Preventive Maintenance

10.1 Inspect thermometers before use. Be sure the liquid column is not separated.

10.2 Be sure glassware is scrupulously cleaned according to GEN-GC.

10.3 Inspect the pH probe for cracks or scratches. Replace the filling solution weekly.

10.4 Troubleshooting – see the manual of the pH meter for specific problems regarding the pH meter.

11) Procedure

11.1 Be sure the analyst has a current Demonstration of Capability and the system has current detection and quantitation studies.

11.2 Print a Responsibility Report from LIMS to determine what samples are available to be run. Prioritize samples to be run based on holding time and due dates. Scan the samples to be analyzed out of storage according to SMO-ICOC. Plan the digestion batch according to ADM-BATCH and the frequency requirements in section 12 of this SOP.

11.3 Heated Digestion

11.3.1 Homogenize and subsample according to ADM-SPLPREP. Place 2.5 ± 0.10 g of the sample into a clean and labeled beaker (for digestion using hot plates) or a labeled digestion vessel (for digestion using stirring hot block). Record the actual weight. Document the ID of the balance used to weigh the sample.

11.3.2 Spike LCSs and MSs (soluble and insoluble) at this time as described in Section 9 and at the frequency in Section 12. Document the spikes added on the benchsheet. Record the ID of the pipette used for spiking.

11.3.3 Measure the pH of the digestion solution with a pH meter. It must be 11.5 or greater to be used. If it is not, discard the solution and make fresh. Record the pH of the solution and the ID of the pH meter on the benchsheet. Add 50 mL of digestion solution to each sample, blank, MS and LCS.

11.3.4 Add approximately 400 mg magnesium chloride and 0.5 mL of phosphate buffer to each sample.

11.3.5 Add the appropriate stir bar to each sample.

11.3.6 Mix each sample thoroughly before placing the beaker on the hotplate.

11.3.6.1 For digestion using hot plates - Turn on the heat to the previously calibrated setting. Place the beakers on the hotplates. Turn on the stirrer. Maintain a temperature range of 90 - 95°C for 60-65 minutes with constant stirring. Record the start time of the digestion. Check the digestion solution temperature of each sample at 0, 30 and 60 minutes using a calibrated alcohol thermometer placed directly in the digestion beaker so that the thermometer is in the beaker spout and the watch glass is placed over the entire beaker. Record the temperature on the benchsheet. Record the end time of the digestion.

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11.3.6.2 For digestion using stirring hot block - Turn on the heat to the previously calibrated setting. For this Environmental Express brand hot block it has been determined that a set point temperature of 112°C provides the proper temperature for samples to be between 90 - 95°C. Place the digestion vessels in the hot block. Turn on the stirrer. Maintain a temperature range of 90 - 95°C for 60-65 minutes with constant stirring. Record the start time of the digestion. Check the digestion solution temperature of each sample at 0, 30 and 60 minutes using a calibrated alcohol thermometer placed directly in the digestion vessel. Plastic thermometer holders (purchased from Environmental Express) can be used to suspend the thermometer in the solution. Record the temperature on the benchsheet. Record the end time of the digestion.

11.3.7 Gradually cool each solution to room temperature. Transfer to b-cups (if digested in beakers), cap, and place in the cooler overnight to allow settling and aid filtration.

11.4 Filtration

11.4.1 Using a 0.45 μm membrane filter, follow the assembly and use procedure for the vacuum filter funnels in GEN-FILTER. Document the filter brand, type, and pore size on the benchsheet. Transfer the digested sample quantitatively to the vacuum filtration apparatus with DI rinses. Rinse the inside of the filter flask and filter pad with DI. Transfer the filtrate and the rinses to a clean, labeled 130-mL B-cup. Record the color of the filtrate on the benchsheet. Cap the cup.

11.4.2 If analysis is not to immediately follow, place the filtered samples in the cooler (0-6°C) and store for up to 7 days (from day of digestion) unless the client has other requirements. On the day of analysis remove the samples from the cooler and allow to warm to room temperature. Continue.

11.5 Standards Preparation

11.5.1 For 7196A - Prepare the standards and references in B-cups. Record the pipettes used. Standards must be prepared and analyzed with each daily run. They do not need to be digested, but they do need the next 2 steps (pH adjustment and dilution).

11.5.2 For 7199 - standards will be prepared by the 7199 analyst with buffered DI and will not need to be pH adjusted and diluted.

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11.6 PH adjustment – record the ID of the pH meter on the benchsheet

11.6.1 For analysis by 7199 - With constant stirring, slowly add concentrated sulfuric acid solution to the beaker dropwise. Adjust the pH of the solution to 9.0-9.5 and monitor the pH with a calibrated pH meter. The buffering capacity of the digestion solution is high, so the first 50 drops of acid will bring the pH down to only about 9.5 to 10.0. Record the pH and the date of adjustment on the bench sheet.

11.6.2 For analysis by 7196A - With constant stirring, slowly add concentrated nitric acid solution to the beaker dropwise. Adjust the pH of the solution to 7.5 ± 0.5 and monitor the pH with a calibrated pH meter. The buffering capacity of the digestion solution is high, so the first 50 drops of acid will bring the pH down to only about 9.5 to 10.0. Go very slowly once the pH reaches about 8.5; at that point it will require only a few drops to go to a pH of 7.5 ± 0.5 - the analyst may wish to switch to 1:1 nitric acid at this point to complete adjustment. If the pH of the digest should drop below 7.0, discard the solution and redigest, and adjust the pH with a dilute nitric acid solution. Record the pH and the date of adjustment on the bench sheet.

Note: The pH adjustment and subsequent steps is time consuming. A single analyst should only adjust about 10 digested samples and complete the colorimetry before adjusting more digested samples. This ensures the samples are analyzed within 1 hour of adjustment. Additional analysts speeds the process and production can be adjusted accordingly.

CAUTION: CO2 will be evolved. This step should be performed in a fume hood.

11.7 Volume Adjustment – Transfer the sample to a graduated cylinder. Adjust the sample volume to 100 mL with DI. Transfer back to the same b-cup. Cap and mix well. This applies to 7196A and 7199 samples and digested QC samples.

11.8 Quantitative Analysis - The sample digestates are now ready to be analyzed. Determine the Cr(VI) concentration in mg/kg by Method 7196A (GEN-7196A) or Method 7199 (GEN-7199). For 7196A, be sure to analyze samples within 1 hour of the time that they are adjusted to a pH of 7.5 + 0.5.

12) Quality Assurance/Quality Control Requirements

12.1 Frequency – One of each of the following are required to be digested with each preparatory batch: MB, LCS (insoluble), DUP, MS (soluble), MS (insoluble).

12.2 Acceptance and corrective action are given in the analytical SOPs.

12.3 As per EPA Method 3060A, if there are QC failures, the entire batch may need re-extracted and reanalyzed. See the analytical SOPs for further details.

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13) Data Reduction and Reporting

13.1 A Copy of the digestion bench sheet is attached.

13.2 Calculations are given in the analytical SOPs.

13.3 Data must be reviewed by the analyst and a peer (supervisor or qualified analyst) using a Data Quality Checklist before the results are validated and reported to the client. Further data review policies and procedures are discussed in ADM-DREV.


Single Laboratory Method Evaluation Data from the EPA Method is available in Table 1.

Reporting limits are based upon an MDL study performed according to ADM-MDL and filed in the MDL binders in the QA office.

Demonstration of Capability is performed upon instrument set-up , whenever a new analyst begins independent analysis, and annually thereafter according to Section 18 below. The documentation of this method performance is retained by the Quality Assurance office.

15) Waste Management and Pollution Prevention

• Hexavalent chromium solutions should be dumped in the red inorganic carboys which will later be emptied by qualified personnel. All other waste can be flushed down the drain with large amounts of water. See SMO-SPLDIS for further information.

• It is the laboratory’s practice to minimize the amount of acids and reagent used to perform this method wherever feasible. Standards are prepared in volumes consistent with methodology and only the amount needed for routine laboratory use is kept on site. The threat to the environment from solvent and reagents used in this method can be minimized when disposed of properly.

• The laboratory will comply with all Federal, State and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions as specified in the EH&S Manual.

16) Corrective Action for Out-of-Control Data

Failure to meet established analytical controls, such as the quality control objectives, prompts corrective action. A QC Flowchart provided in the analytical SOPs describes the corrective actions for out of control QC.

17) Contingencies for Handling Out-of-Control or Unacceptable Data

If a quality control measure is found to be out of control, and the data is to be reported, all samples associated with the failed quality control measure shall be reported with the appropriate data qualifier(s).

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18) Training

18.1 Read current SOP and applicable methodologies. Demonstrate a general understanding of the methodology and chemistry. Follow Training Policies in the SOP for Training (CE-QA003).

18.2 Observe Sample Preparation and Analysis. Follow Training Plan Form.

18.3 Participate in the methodology, documentation, and data reduction with guidance.

18.4 Perform the analysis independently and show Initial Demonstration of Capability (IDC) by analyzing 4 replicates of a known mid-range standard in succession before client samples are analyzed. If recovery is within acceptable limits, complete IDC certificate and Training Plan Form and file with QA. Continuing Demonstration of Capability (CDC) will be demonstrated annually using a PE sample, single blind, or a new 4 replicate study. Demonstrate Competency by performing the analysis independently.

19) Method Modifications

The method says to mix the sample 5 minutes on the hotplate before turning on the heat. Instead, the lab mixes the sample thoroughly with the reagents before placing the sample beaker on the pre-heated hotplate. This modification reduces the amount of time spent with samples on the hotplates and increases the number of samples which may be analyzed in a day without affecting the quality of the analysis.


• Updated to ALS format – removed CAS throughout.

• Added information for stirring Hotblock.

21) References

• Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, USEPA SW-846, 3060A, December 1996.

22) Attachments

• Digestion Benchsheets

• Table 1 – Single Laboratory Method Evaluation Data

• 3060 Flowchart

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Soil Sample Preparation for the Determination of Radionuclides

SOP Effective 10/21/93 GL-RAD-A-021 Rev 20

Revision 20 Effective August 2012 Page 1 of 12

GEL LABORATORIES, LLC

2040 Savage Road Charleston SC 29407

This document is controlled when an original Set ID number is stamped on the front cover page (1).

Uncontrolled documents do not bear an original Set ID number.

VERIFY THE VALIDITY OF THIS SOP EACH DAY IN USE


FOR

SOIL SAMPLE PREPARATION

FOR THE DETERMINATION OF RADIONUCLIDES

(GL-RAD-A-021 REVISION 20)

PROPRIETARY INFORMATION

This document contains proprietary information that is the exclusive property of GEL

Laboratories, LLC (GEL). No contents of this document may be reproduced or otherwise

used for the benefit of others except by express written permission of GEL.

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TABLE OF CONTENTS

1.0 STANDARD OPERATING PROCEDURE FOR THE SOIL SAMPLE PREPARATION

FOR THE DETERMINATION OF RADIONUCLIDES .................................................. 3

2.0 METHOD OBJECTIVE AND APPLICABILITY............................................................. 3

3.0 SUMMARY........................................................................................................................ 3

4.0 SAFETY PRECAUTIONS AND HAZARD WARNINGS ............................................... 3

5.0 APPARATUS AND MATERIALS.................................................................................... 3

6.0 SAMPLE COLLECTION AND PRESERVATION .......................................................... 4

7.0 EQUIPMENT AND INSTRUMENT MAINTENANCE................................................... 4

8.0 SAMPLE PREPARATION PROCEDURES ..................................................................... 4

9.0 CALCULATIONS AND DATA REDUCTION METHODS............................................ 7

10.0 QUALITY CONTROL REQUIREMENTS ....................................................................... 7

11.0 CALIBRATION ................................................................................................................. 7

12.0 RECORDS MANAGEMENT AND DOCUMENT CONTROL ....................................... 7

13.0 LABORATORY WASTE HANDLING AND DISPOSAL............................................... 8

14.0 REFERENCES ................................................................................................................... 8

15.0 HISTORY ........................................................................................................................... 8

APPENDIX I: HGEO GROSS SAMPLE PRE-TREATMENT......................................... 9

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1.0 STANDARD OPERATING PROCEDURE FOR THE SOIL SAMPLE PREPARATION

FOR THE DETERMINATION OF RADIONUCLIDES

2.0 METHOD OBJECTIVE AND APPLICABILITY

This standard operating procedure provides the necessary instructions to conduct the

preparation of soil samples for radionuclide determination.

3.0 SUMMARY

This procedure involves drying the soil at a temperature between 103 and 105 ºC. If that

temperature would volatilize any components for which an analysis has yet to be run, a

separate aliquot must be set aside for such analyses.

4.0 SAFETY PRECAUTIONS AND HAZARD WARNINGS

4.1 Personnel performing this analytical procedure are trained in and follow the safe

laboratory practices outlined in the Safety, Health, and Chemical Hygiene Plan,

GL-LB-N-001.

4.2 Personnel handling radioactive materials are trained in and follow the procedures

outlined in GL-RAD-S-004 for Radioactive Material Handling.

4.3 Personnel handling biological materials are trained in and follow the procedures

outlined in GL-RAD-S-010 for The Handling of Biological Materials.

4.4 If there is any question regarding the safety of any laboratory practice, stop

immediately, and consult qualified senior personnel such as a Group or Team

Leader.

5.0 APPARATUS AND MATERIALS

5.1 Apparatus and Equipment

5.1.1 Metal cans, approximately quart and pint size

5.1.2 Steel balls, approximately 1" and 3/4" diameter

5.1.3 Sieve screens, 28 mesh

5.1.4 Paper funnels

5.1.5 100 cc aluminum cans

5.1.6 Aluminum loaf pans

5.1.7 SPEX steel grinding containers (various sizes)

5.1.8 Assorted tools and labware

5.2 Reagents, Chemicals, and Standards

5.2.1 Sand, clean

5.2.2 Deionized water (DI water)

5.3 Instrumentation

5.3.1 Paint can shaker, heavy duty

5.3.2 Analytical balance

5.3.3 SPEX Model 8515-115 Shatterbox

5.3.4 Drying oven

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5.3.5 Hydraulic press

5.3.6 Retsch, Model BB-51, Jaw Crusher

5.3.7 Automatic or manual can sealer

6.0 SAMPLE COLLECTION AND PRESERVATION

A representative sample must be collected from a source of soil and should be large

enough (50 to 100 g) so that adequate aliquots can be taken to obtain the required

sensitivity. The container of choice should be plastic over glass to prevent loss due to

breakage during handling. No preservation is required for solid samples.

7.0 EQUIPMENT AND INSTRUMENT MAINTENANCE

7.1 Refer to the technical manual provided with the paint shaker for information

regarding equipment maintenance.

7.2 Refer to Instruction Manual for SPEX Shatterbox and Retsch Jaw Crusher

operating instructions.

7.3 The analytical balance should be cleaned after use.

7.4 Refer to operating instructions for automatic or manual can sealer for information

regarding equipment maintenance.

7.4.1 After receipt of new can sealer or when maintenance is performed on

canner that could affect the proper sealing of the 100 cc gamma cans,

perform a leak test on a can as follows:

7.4.1.1 Fill gamma can with water and seal.

7.4.1.2 Apply pressure on top and bottom of can and inspect for any

visible signs of leakage.

8.0 SAMPLE PREPARATION PROCEDURES

8.1 Label a clean metal container with the laboratory sample number.

8.2 Weigh container. Record weight into the computerized soil prep balance log.

8.3 Transfer a representative aliquot from the sample to the labeled container.

8.3.1 When the amount of sample to be dried is not the entire contents of the

sample container, refer to section 6.6 of SOP GL-LB-E-029 to ensure a

representative sample aliquot is taken. This also ensures that the sample

remaining is representative of the whole sample.

8.3.2 If the sample contains extraneous materials (i.e. rocks, twigs, vegetation)

this shall be documented in the batch case narrative.

NOTE: Sample is dried at 103 to 105 C. If this temperature will volatilize any

component for an analysis that has yet to be run, a separate aliquot must be set aside for

such analysis.

8.4 Enter the pre-oven sample weight into the computerized soil prep balance log.

This weight represents the wet sample weight and container weight.

8.5 Place the container in a drying oven at a temperature between 103 and 105 C for

a minimum of four hours. (Normally overnight.)

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NOTE: The time required to obtain a dry sample will vary depending on the type of

material, size of sample, oven type and capacity, and other factors. The influence of

these factors generally can be established by good judgment, experience with the

materials being tested, and the apparatus being used.

8.6 Using heat resistant gloves, remove the sample from the oven and allow to cool.

8.7 Record weight into the computerized soil prep balance log. Replace sample in

drying oven for a minimum of one hour.

8.8 Repeat step 8.7 until a constant weight is obtained. A constant weight is defined

as a weight difference of less than about 0.1% (i.e. for a 20 g aliquot, the change

in weight shuld be less than 0.02 g).

8.9 Homogenize the sample. This is normally accomplished by placing a lid on the

container and placing the container in the industrial paint shaker. Depending on

the matrix of the soil, it may be necessary to add several stainless steel balls

inside the container to assist in homogenizing the sample. The length of time the

sample remains on the shaker is dependent on the matrix of the sample, and

normally ranges from 5 to 10 minutes. For solid samples that are composed of

large particles, it may be necessary to reduce the particle size before

homogenizing. This can be accomplished by placing the larger particles in the

hydraulic press and applying enough pressure to break the particles into smaller

pieces.

8.10 Remove the metal container from the shaker and allow to settle for several

minutes.

8.11 Place the container in the sample preparation hood and remove the lid. If

stainless steel balls were added to the container, they should now be removed.

The stainless steel balls are discarded.

8.12 Determine an appropriate aliquot based on the analysis required. Normally,

depending upon the required analysis, the sample will be passed through a 28

mesh sieve screen. For clients that require a smaller particle size, continue

homogenizing samples per section 8.15.

8.13 Discard the unused portion of sample into the appropriate waste container (i.e.

rocks or organic material). The soil sample is now ready for radiochemical

analysis.

8.14 Place sample in appropriate containers (i.e. plastic bottle or vial, gamma can).

NOTE: If preparing a 100 cc gamma can, it is important that the can is properly sealed

to ensure Ra-226 is quantified correctly. Ra-226 in soil samples is quantified by one of its

daughter products (Bi-214). Ra-226 decays to Bi-214 through Rn-222, which is a gas,

and must be isolated inside the can in order for equilibrium to be re-established.

8.14.1 For proper sealing of gamma can:

8.14.1.1 Place lid on 100 cc can and place can on base plate of the

automatic or manual can sealer.

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8.14.1.2 Raise the can until it is clamped firmly between the base plate

and chuck by turning the can lifter handle as far as possible to

the right until the handle locks itself against the frame.

8.14.1.2.1 If using the automatic can sealer push the on button.

The flywheel will turn until the can sealing is

complete.

8.14.1.2.2 If using the manual can sealer, turn the flywheel 21

turns until the second operational roll returns to its

normal position, away from the chuck.

8.14.1.3 Lower the can by turning the can lifter handle to the left.

Remove the sealed can from the base plate.

8.14.1.4 Visually inspect can after sealing for any defects. If defects are

noticed that may affect the proper sealing of the can, remove

contents from can and start over with a new can.

8.15 Shatter Box (200 mesh sample)

8.15.1 Take a portion of remaining sample (more than enough to complete the

requested analysis) and further homogenize sample to approximately 200

mesh. This is accomplished by pulverizing sample in the shatterbox.

NOTE: The approximately 200 mesh is determined based on particle size study in

shatterbox instruction manual.

8.15.2 Pulverize sample for a minimum of 5 minutes.

NOTE: Refer to Shatterbox Instruction Manual for operating procedure.

8.15.3 To prevent cross-contamination the dish and puck must be decontaminated

prior to pulverizing the next sample.

8.15.3.1 Decontaminate the dish and puck by filling with

approximately50 g of sand. Replace the lid.

8.15.3.2 Place the shatterbox in operation for approximately 1 to 2

minutes. Empty the sand from the container.

8.15.3.3 Dampen a clean paper towel with DI water and wipe the

dish, puck and lid to ensure that all traces of sand are

removed.

8.15.3.4 To check for contamination, perform a smear survey of

dish and puck after each dish and puck decontamination with

sand, and submit to Radiation Safety for counting.

8.15.3.5 A decontamination blank is analyzed monthly for gross

alpha, beta, and gamma activity. The results of these

analyses will be compared to historical data. When a

decontamination blank is analyzed, it is pulverized post

cleaning.

30-Sep-2013








NOTE: To prevent corrosion, keep the entire container assembly dry.

8.15.4 Record all samples and decontamination blanks in the shatterbox logbook.

8.16 Pulverizer

8.16.1 Use the sample jaw crusher to prepare medium to extremely hard

substances having a maximum input grain size of 35 mm.

NOTE: Refer to Retsch Jaw Crusher Type BB-51 Operating Instructions manual

for operating procedure.

8.16.2 To prevent cross-contamination, the jaw crusher must be decontaminated

prior to processing the next sample. Decontaminate the jaw crusher by

processing approximately 200 g of pre-dried lava rock having a maximum

input grain size of 35 mm. A decontamination blank is analyzed monthly

for gross alpha, beta, and gamma activity. The results of these analyses

will be compared to historical data.

9.0 CALCULATIONS AND DATA REDUCTION METHODS

The electronic balance program provides documentation of all necessary raw data.

Weights in AlphaLIMS are recorded to three places past the decimal point (Ex: 6.738,

314.197…).

9.1 If client requests results to be reported “as received” (based on wet weight),

analysts will correct the “dry” aliquots back to wet weights using the

“weight/loss aliquot correction report” link in AlphaLIMS. This report will be

included, if necessary, in each analytical batch’s raw data.

10.0 QUALITY CONTROL REQUIREMENTS

10.1 Method Specific Quality Control Requirements

10.1.1 When possible (i.e., there is sufficient sample available) for gamma

analysis, a separate container will be prepared for counting to meet the

duplicate sample requirement.

10.1.2 Refer to the specific isotope operating procedure for instructions

concerning method quality control requirements.

10.2 Actions Required if the Quality Control Requirements Are Not Met

If any of the quality criteria cannot be satisfied, the analyst should inform the

group leader and initiate a Data Exception Report as outlined in GL-QS-E-004 for

Documentation of Nonconformance Reporting and Dispositioning and Control of

Nonconforming Items.

11.0 CALIBRATION

11.1 Balances are calibrated annually and verified daily in accordance with GL-LB-E-

002.

11.2 Temperature monitoring devices are verified in accordance with GL-QS-E-007.

12.0 RECORDS MANAGEMENT AND DOCUMENT CONTROL

30-Sep-2013








All data are maintained as quality records in accordance with GL-QS-E-008 for Quality

Records Management and Disposition.

13.0 LABORATORY WASTE HANDLING AND DISPOSAL

Laboratory waste is handled and disposed in accordance with the Laboratory Waste

Management Plan, GL-LB-G-001.

14.0 REFERENCES

14.1 ASTM C999-05, “Standard Practice for Soil Sample Preparation for

Determination of Radionuclides,” 1993 Annual Book of ASTM Standards, Vol

12.01, 2005.

14.2 Laboratory Sub-Sampling Procedure, GL-LB-E-029.

14.3 ASTM D6323-98 (2003) “Standard Guide for Laboratory Subsampling of Media

Related to Waste Management Activities.”

14.4 EPA’s “Guidance for Obtaining Representative Laboratory Analytical

Subsamples from Particulate Laboratory Samples”, EPA/600/r-03/027, November

2003.

15.0 HISTORY

Revision 20: Section 9.1 revised for clarification to comply with DOECAP audit finding.

Revision 19:Added client specific prep procedure as an appendix.

Revision 18: Changed 8.14-8.17 to 8.15-18.17 in section 8.12.

30-Sep-2013








APPENDIX I: HGEO GROSS SAMPLE PRE-TREATMENT

This proposed procedure is for the preparation of SSFL soil samples for Hydrogeologic,

Inc.

1.) Cover an area of bench top, within a HEPA filtered enclosure, with clean paper.

Transfer the total raw sample to the paper and spread sample evenly across the

surface. Samples may be contained in more than one sample container.

2.) Remove cultural/man-made materials from the sample if applicable, photograph, and

place in a labeled container for storage. If no cultural/man/made materials are found,

no photograph is required, provided that the laboratory documentation clearly notes

that no such objects were found. Notify Project Manager if cultural/man-made

materials are found in the samples.

3.) Label a clean metal container with the laboratory sample number. When large

amounts of soil are being processed, samples may be dried in aluminum pans to

improve effectiveness of complete drying. Note: Samples may be split into more

than one drying vessel. Record weights separately until the sample is recombined.

4.) Weigh the containers and record weights into the soil prep balance log.

5.) Transfer the entire sample to the labeled container. When the amount of sample to be

dried is not the entire contents of the sample container, document via a Data

Exception Report. Any sample removed in this manner shall be done by taking a

grab sample to minimize any loss of potentially volatile radionuclides.

6.) Enter the pre-oven sample weight into the soil prep balance log. This weight

represents the wet sample weight and container weight.

7.) Place the container(s) in a drying oven at a temperature between 103 and 105 °C for

a minimum of four hours. Record the time the sample was placed in the oven.

8.) Using protective heat resistant gloves remove the sample from the oven and allow

cooling. Record the time the sample was removed from the oven.

9.) Record the weight in the soil prep balance log and place the sample back in the

drying oven for a minimum of one hour. Record the time the sample was returned to

the oven. Record the time the sample was removed from the oven for each interval.

10.) Repeat steps 8 and 9 until a constant weight is obtained. A constant weight is

achieved when two subsequent weights agree within 1%.

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11.) Break up the sample in preparation for passing through the sieves with the process.

Transfer sample to an appropriate number of 1 gallon paint cans. Add 6- 1" stainless

steel balls to each paint can to aid in the breakup of the samples. NOTE: Paint cans

should not be filled above approximately 3/4 full. Overfilling will reduce the

effectiveness of sample blending. Place the paint cans on the industrial paint can

shaker for 5-10 minutes.

12.) Remove the container(s) from the paint can shaker and allow settling for several

minutes.

13.) Place the container(s) in the sample in a ventilated preparation hood and remove the

lid. If stainless steel balls were added to the container(s), they should now be

removed and discarded.

14.) Pass entire dried sample through a 4-mesh sieve. Transfer material that will not pass

through into a labeled container for storage. The analyst will evaluate the material

to determine if they may be further broken up in order to be passed through the 4-

mesh sieve.

15.) Pass the entire dried sample through a 28-mesh sieve. Any sample not passing

through the 28-mesh sieve must be processed until it passes through the 28-mesh

sieve. Contact the Group leader if these criteria cannot be met.

16.) Place sample back into the paint cans and mix on the paint can shaker for 5-10

minutes.

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17.) From the <28-mesh sample, use the 'Cone and Quartering' method described below

to remove a representative sample fraction for gamma analysis (~2000 grams).

18.) Cone and Quartering' method - Sample is emptied out onto a non-contaminating

smooth surface. Material is piled into a cone with a flattened top surface. Two top-

to-bottom cuts are made through the cone at perpendicular angles to form four equal

portions, or quarters. Two opposite quarters are compiled into a new cone, and the

process is repeated until the proper sample mass is obtained. When sub-sampling

using this method it is important to remove the entire quarters to be used. Process

enough sample to prepare a new 1-Liter Marinelli beaker (~1600-1700 grams) and

100cc gamma can (~160-180 grams) geometries for gamma analysis.

19.) Record the weight of the gamma aliquots in the soil prep balance log. Some samples

may need an equal portion of sample for archiving as noted by the project manager.

20.) Take a portion of remaining sample using the ‘Cone and Quartering’ method(more

than enough to complete the requested analysis) and further homogenize sample to

approximately 200 mesh. This is accomplished by pulverizing sample in the

shatterbox (puck mill).i

Note: Some samples may be designated to prepare an equal portion of sample for

archiving.

i The approximately 200 mesh is determined based on particle size study in shatterbox instruction manual. The number of replicates included in the study was determined based on guidance provided in chapter 6 of the MARLAP manual (Level B validation).

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21.) Pulverize sample for 5 minutes. Refer to Shatterbox Instruction Manual for

operating procedure.

22.) To prevent cross-contamination the dish and puck must be decontaminated prior to

running the next sample. Decontaminate the dish and puck by filling with

approximately 50 g of sand. Replace the lid and operate the shatterbox for 2

minutes. Empty the sand from the container.

23.) Dampen a clean paper towel with DI water and wipe the dish, puck and lid to ensure

that all traces of the sand are removed. To check for gross contamination, perform a

smear survey of dish and puck and submit to radiation safety office for counting.

24.) To monitor for low level contamination, process blanks will be analyzed. The

process blanks will consist of an ICP/MS analysis for U-238 on DI water rinses of

the grinding containers (500 mLs). Acceptable results of the blanks shall be less

than MDL. Should a blank indicate the presence of U-238 at a level >MDL, it shall

be documented and a review conducted to determine the impact on any data

produced using the container in question.

Record all samples and decontamination blanks in the shatterbox logbook.

30-Sep-2013

The Determination of Gamma Isotopes

SOP Effective Date: 2/4/92 GL-RAD-A-013 Rev 25

Revision 25 Effective February 2013 Page 1 of 9


2040 Savage Road Charleston, SC 29407





FOR

THE DETERMINATION

OF

GAMMA ISOTOPES

(GL-RAD-A-013 REVISION 25)

APPLICABLE TO METHODS:

EPA 600/4-80-032 Method 901.1

DOE EML HASL-300 Section 4.5.2.3

DOE EML HASL-300 Ga-01-R


This document contains proprietary information that is the exclusive property of GEL Laboratories,

LLC (GEL). No contents of this document may be reproduced or otherwise used for the benefit of

others except by express written permission of GEL.

30-Sep-2013








TABLE OF CONTENTS

1.0 STANDARD OPERATING PROCEDURE FOR THE DETERMINATION OF

GAMMA ISOTOPES ......................................................................................................... 3

2.0 METHOD OBJECTIVE, PURPOSE, AND SUMMARY ................................................. 3

3.0 METHOD SCOPE, APPLICABILITY, AND DETECTION LIMIT ................................ 3

4.0 METHOD VARIATIONS .................................................................................................. 4

5.0 DEFINITIONS.................................................................................................................... 4

6.0 INTERFERENCES............................................................................................................. 4

7.0 SAFETY PRECAUTIONS AND WARNINGS................................................................. 4

8.0 APPARATUS, EQUIPMENT, AND INSTRUMENTATION .......................................... 5

9.0 REAGENTS, CHEMICALS, AND STANDARDS........................................................... 5

10.0 SAMPLE HANDLING AND PRESERVATION .............................................................. 6

11.0 SAMPLE PREPARATION ................................................................................................ 6

12.0 QUALITY CONTROL SAMPLES AND REQUIREMENTS .......................................... 8

13.0 INSTRUMENT CALIBRATION, STANDARDIZATION, AND PERFORMANCE...... 8

14.0 ANALYSIS AND INSTRUMENT OPERATION............................................................. 8


16.0 DATA RECORDING, CALCULATION, AND REDUCTION METHODS.................... 8

17.0 DATA REVIEW, APPROVAL, AND TRANSMITTAL .................................................. 9

18.0 RECORDS MANAGEMENT ............................................................................................ 9

19.0 LABORATORY WASTE HANDLING AND DISPOSAL............................................... 9

20.0 REFERENCES ................................................................................................................... 9

21.0 HISTORY ......................................................................................................................... 10

30-Sep-2013








1.0 STANDARD OPERATING PROCEDURE FOR THE DETERMINATION OF GAMMA

ISOTOPES

2.0 METHOD OBJECTIVE, PURPOSE, AND SUMMARY

2.1 This standard operating procedure (SOP) provides the necessary instructions to

conduct the analysis for gamma isotopes in water, soil, urine, filters, drinking

water and miscellaneous matrices.

2.2 Water samples are typically counted in Marinelli beakers. Soil samples are

typically sealed in aluminum cans, which can be counted immediately if Ra-226

is not desired. If Ra-226 is desired, the sealed can is set aside for minimum of 20

days to allow equilibrium between Rn-222 and Bi-214 to become re-established.

Ra-226 is then quantified using the 609 keV line of Bi-214.

2.3 This method is based on the source method EPA 600/4-80-032 “Prescribed

Procedures for Measurement of Radioactivity in Drinking Water,” August 1980,

Method 901.1, and the Department of Energy (DOE) EML Procedures Manual

source method for Gamma PHA in environmental samples, HASL-300 Section

4.5.2.3 and Ga-01-R, Gamma Radioassay.

2.4 This SOP is applicable for analyzing samples that contain radionuclides emitting

gamma photons with energies ranging from about 5 to 2000 keV (including I-

131).

3.0 METHOD SCOPE, APPLICABILITY, AND DETECTION LIMIT

3.1 Minimum Detectable Activity (MDA): The MDA is based upon sample volume,

Compton background, instrument efficiency, count time, and other statistical

factors, as well as specific isotopic values such as abundance and half-life. A

typical detection limit is 10 pCi/L or 0.1 pCi/g (based on Cs-137). The MDA for

drinking water samples is 10 pCi/L (based on Cs-137).

3.2 Method Precision: Typical Relative Percent Difference (RPD) is 20% or less or

100% or less if the activity is less than five times the MDA.

3.3 Method Bias (Accuracy): The method accuracy requirement for gamma,

measured by running a Laboratory Control Sample (LCS) with each batch, is 25%

of the true value. For drinking water samples, laboratory fortified blanks (LFB,

equivalent to LCS) recoveries should be between 90-110% of the known value.

3.4 Procedures contained in this SOP may be used to analyze REMP samples.

3.5 Analysts training records are maintained as quality records as outlined in GL-QS-

E-008. Analysts training and proficiency in the method is outlined in the

Employee Training SOP GL-HR-E-002.

3.6 For drinking water samples, analyst initial and ongoing demonstrations of

proficiency will follow critical elements for radiochemisrtry, chapter VI, section

1.5, of The Manual for the Certification of Laboratories Analyzing Drinking

Water (reference 20.5).

3.7 Sensitivity studies will follow critical elements for radiochemistry, chapter VI,

section 7.3 of The Manual for the Certification of Laboratories Analyzing

Drinking Water (reference 20.5).

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4.0 METHOD VARIATIONS

4.1 Some variations may be necessary due to special matrices encountered in the lab.

These variations may be used with approval from a Group Leader or Team

Leader. Variations to a method will be documented with the analytical raw data.

4.2 Filter samples can either be counted directly, or digested prior to counting. If

filters are digested, they are digested in accordance with GL-RAD-A-026.

4.3 No method modifications are permitted for drinking water samples.

5.0 DEFINITIONS

5.1 National Institute of Standards and Technology (NIST): For the purpose of this

method, the national scientific body responsible for the standardization and

acceptability of analyte solutions.

5.2 Deionized (DI) water: Type I water.Refer to GL-LB-E-016.

5.3 AlphaLIMS: GEL’s Laboratory Information Management System.

5.4 Batch: Environmental samples that are prepared and/or analyzed together with the

same process and personnel, using the same lot(s) of reagents.

5.5 Method Blank (MB): A sample of a matrix similar to the batch of associated

samples (when available) that is free from the analytes of interest and is processed

simultaneously with and under the same conditions as samples containing an

analyte of interest through all steps of the analytical procedures.

5.6 Laboratory Duplicate (DUP): For soils, when sufficient sample is available, a

separate duplicate will be prepared. For liquid samples and when sufficient sample

is not available for solids, an independent count of the sample container will be

performed to show precision.

5.7 Laboratory Control Sample (LCS): A sample matrix, similar to the batch of

associated samples (when available) that is free from the analytes of interest,

spiked with verified known amounts of analytes from a source independent of the

calibration standards or a material containing known and verified amounts of

analytes. The LCS is equivalent to a Fortified Blank in the EPA drinking water

compliance manual (See to section 20.5).

6.0 INTERFERENCES

6.1 Some gamma isotopes emit gamma lines that may overlap with other isotopes. If

the energies of the two isotopes are within the energy tolerance setting, the peaks

may not be resolvable and may give a positive bias to the result. This problem is

minimized by careful review of the peak search.

6.2 Soil samples may vary in density from the standard used for calibration. A

density correction is applied to the “CAN” geometry. This correction was

determined using solids with weights varying between 54 g and 192 g.

7.0 SAFETY PRECAUTIONS AND WARNINGS

7.1 Keep hands free from moving parts of canning device and gamma shields.

30-Sep-2013








7.2 Personnel performing this analytical procedure are trained in and follow the safe

laboratory practices outlined in the Safety, Health and Chemical Hygiene Plan,

GL-LB-N-001.

7.3 Personnel handling radioactive materials are trained in and follow the procedures

outlined in GL-RAD-S-004 for Radioactive Material Handling.

7.4 Personnel handling biological materials are trained in and follow the procedures

outlined in GL-RAD-S-010 for The Handling of Biological Materials.

7.5 If there is any question regarding the safety of any laboratory practice, stop

immediately, and consult qualified senior personnel such as a Group or Team

Leader.

8.0 APPARATUS, EQUIPMENT, AND INSTRUMENTATION

8.1 Ancillary Equipment

8.1.1 100 cc aluminum cans with lids for soil and miscellaneous samples

8.1.2 10 cc Gelman Sciences Petri dish for soil, filters and miscellaneous samples

8.1.3 2 L and 500 mL Marinelli beakers for water samples

8.1.4 Air displacement pipettes

8.1.5 Can sealing tool

8.1.6 Graduated cylinder

8.1.7 25 cc VWR Petri for soil and miscellaneous samples

8.1.8 250 mL plastic jar for filters, soil, and miscellaneous samples

8.1.9 Hot plate

8.1.10 Teflon beakers and lids

8.1.11 1 L Marinelli beaker for soil samples

8.2 Instrumentation

8.2.1 High purity germanium detector, with associated electronics and data

reduction software

8.2.2 NaI Detector with associated electronics and data reduction software

8.2.3 Top loader balance

9.0 REAGENTS, CHEMICALS, AND STANDARDS

9.1 NIST traceable mixed gamma standard in 100 cc aluminum can

9.2 NIST traceable mixed gamma standard in 2.0 L Marinelli beaker


9.4 NIST traceable mixed gamma standard in Gelman Sciences 10 cc Petri dish

9.5 NIST traceable mixed gamma standard in 13, 47 mm glass fiber filter composites in

Gelman Sciences Petri dish.

9.6 NIST traceable mixed gamma standard in 0.4 L jar

9.7 NIST traceable mixed gamma standard in 0.25 L jar

9.8 NIST traceable mixed gamma standard in 1, 47 mm glass fiber filter

30-Sep-2013








9.9 NIST traceable mixed gamma standard in Impregnated Charcoal Sample Cartridge.

9.10 NIST traceable mixed gamma standard in VWR (53 mm x 15 mm) Petri dish

(approximately 25 cc)

9.11 NIST traceable mixed gamma standard in aqueous solution


9.13 NIST traceable mixed gamma standard in 20 mL liquid scintillation vial

9.14 16 M Nitric acid, reagent grade (HNO3)

9.15 49% Hydrofluoric acid (HF)

9.16 12 M Hydrochloric acid, reagent grade (HCl)

9.17 5% Boric acid: Dissolve 50 g of H3BO3 per liter of DI water.

9.18 Nitric acid (8 M HNO3): Prepare by cautiously adding a measured volume of

concentrated nitric acid to an equal volume of DI water.

10.0 SAMPLE HANDLING AND PRESERVATION

10.1 For soil samples, 500 g of sample should be collected, preferably in a plastic

container to avoid breakage.

10.2 For water samples, 2 L of sample should be collected in a plastic container and

preserved to a pH < 2 with nitric acid.

10.2.1 Before beginning an analysis, the analyst should check the sample pH by

removing a minimal amount of sample with a transfer pipette and placing

it on a pH strip. DO NOT insert pH strip into sample container. If the

sample is received with a pH greater than 2, the analyst should contact

the Group Leader or Team Leader.

NOTE: If the analysis is requesting I-131 (or any other iodine isotopes) Analysis

without preserving is acceptable. If a sample is preserved with acid

without stabilizing the iodine, Iodine may volatilize and escape the

solution as a gas.

10.2.2 If approved by the client, the analyst should adjust the pH with nitric acid

to a pH < 2. If the sample pH is adjusted, let the sample sit in the

original container for a minimum of 24 hours before analysis. This

acidification should be documented on a batch history sheet and attached

to the batch paperwork.

10.3 For filters no preservation is necessary.

11.0 SAMPLE PREPARATION

11.1 Solid Sample Preparation.

11.1.1 Prepare the sample for gamma counting in accordance with SOP GL-RAD-

A-021, Soil Sample Preparation for the Determination of Radionuclides.

11.1.2 Fill the appropriate container with sample prepared from step 11.1.1

using the following steps as a guideline:

11.1.2.1 If Ra-226 analysis is required, the sample is placed in a 100 cc

can for in-growth.

30-Sep-2013








NOTE: It is recommended that in-growth be allowed 20 days to quantify

Ra-226. Shorter ingrowth periods can be used at the request of the

client. However, shorter in-growth periods may decrease the accuracy of

the data. If there is insufficient mass of sample to fill the 100 cc can,

contact the Team or Group Leader.

11.1.2.2 If sufficient mass is available, homogenized samples should be

placed in the 100 cc can. Determine the net weight of the

sample. If the net weight is less than 54 g or greater than 192

g, contact the Team or Group Leader to determine the

appropriate counting container. Record sample weight and

date in AlphaLIMS and on sample container.

11.1.2.3 If there is insufficient sample to fill the 100 cc can, place

sample in the 10 cc or 25 cc Petri dish, cap and seal. Record

sample weight and date in AlphaLIMS and on sample

container.

11.1.2.4 If there is insufficient sample to fill the 10 cc Petri dish,

perform the following digestion process:

11.1.2.4.1 Weigh out an appropriate aliquot into a labeled

Teflon beaker. Record this weight on the Queue

sheet.

11.1.2.4.2 Add 10 mL of concentrated nitric acid to each

sample.

11.1.2.4.3 Place samples on medium heat (approximately

300 F) and cover each sample with a Teflon lid.

Reflux all samples for 30 minutes.

11.1.2.4.4 Remove Teflon lids and add 5 mL concentrated

hydrochloric acid and 10 mL hydrofluoric acid to

each sample. Cover samples and reflux for 120

minutes.

11.1.2.4.5 Remove Teflon lids and allow samples to

evaporate to dryness.

11.1.2.4.6 Add 5 mL of concentrated nitric acid and

evaporate to dryness.

11.1.2.4.7 Repeat Step 11.1.2.4.6.

11.1.2.4.8 Add 5 mL of concentrated nitric acid to the dry

samples. Add 1 mL of 5% boric acid. Place the

samples back on the hot plate long enough so that

the dried sample dissolves into solution.

11.1.2.4.9 Transfer solution to a 250 mL gamma container

and dilute to 200 mL. Record the original sample

mass and diluted volume on sample container.

30-Sep-2013








Record the original sample mass on batch Queue

sheet.

11.2 Water Sample Preparation

11.2.1 Place the appropriate labeled Marinelli beaker (typically 500 mL or 2 L)

on a balance and tare the balance.

11.2.2 If less than approximately 1.1 L is available, sample should be poured

into a 500 mL Marinelli beaker.

11.2.3 Transfer the appropriate volume to the tared container and record the

volume of the sample on the Queue sheet.

NOTE: If there is insufficient sample to fill the Marinelli, record the exact

amount of sample volume on the container and on the Queue sheet. Dilute the

sample to the appropriate volume to maintain the calibration geometry. Record

the volume the sample was diluted to on the sample container, also.

11.2.4 The MB should be recorded on the Queue sheet to be the same aliquot as

the largest sample in the batch. An empty Marinelli beaker should be

labeled as the MB and submitted with each batch of samples.

11.2.5 Submit the Marinellis and completed paperwork to the count room for

gamma counting analysis.

11.3 Urine Sample Preparation

11.3.1 Refer to GL-RAD-B-030.

11.4 Preparation of Miscellaneous Matrices

11.4.1 Prepare the sample in accordance with GL-RAD-A-026 for The

Preparation of Special Matrices for the Determination of Radionuclides.

11.4.2 If sample(s) was (were) received from the client in a container that

matches a calibrated geometry, a direct count of the sample can be

performed.

12.0 QUALITY CONTROL SAMPLES AND REQUIREMENTS

Refer to GL-RAD-D-003.

13.0 INSTRUMENT CALIBRATION, STANDARDIZATION, AND PERFORMANCE

Refer to GL-RAD-I-001.

14.0 ANALYSIS AND INSTRUMENT OPERATION




16.0 DATA RECORDING, CALCULATION, AND REDUCTION METHODS

Data recording, calculation and reduction take place in accordance with SOP GL-RAD-

D-003 and GL-RAD-D-006.

30-Sep-2013








17.0 DATA REVIEW, APPROVAL, AND TRANSMITTAL

Data are reviewed and packaged in accordance with GL-RAD-D-003 for Data Review,

Validation, and Data Package Assembly.

18.0 RECORDS MANAGEMENT

Records generated as a result of this procedure are maintained as Quality Documents in

accordance with GL-QS-E-008 for Quality Records Management and Disposition.


Radioactive samples and material shall be handled and disposed of as outlined in the

Laboratory Waste Management Plan, GL-LB-G-001.

20.0 REFERENCES

20.1 USEPA. Prescribed Procedures for Measurement of Radioactivity in Drinking

Water, Method 901.1, August 1980.

20.2 Canberra Nuclear Genie System Spectroscopy, Applications and Display User's

Guide, Vol. I and II, May 1991.

20.3 DOE EML Procedures Manual, HASL-300, 27th

Edition.

20.4 DOE EML Procedures Manual, HASL-300, 28th

Edition.

20.5 Manual for the Certification of Laboratories Analyzing Drinking Water. Criteria

and Procedures Quality Assurance. Fifth Edition EPA 815-R-05-004 January

2005.

21.0 HISTORY

Revision 25: Type II to type I water.

Revision 24: Changed recovery limit for laboratory fortified blank from 90-100% to 90-

110% in section 3.3.

Revision 23:Procedure updated to include requirements for drinking water samples.

Revision 22: Updated ingrowth period for Ra-226 to 20 days.

Revision 21: SOP revised to add Ra-226, NIST traceable gamma standards, and other

clarifications.

30-Sep-2013

Determination of Metals by ICP-MS SOP Effective 11/95 GL-MA-E-014 Rev 25

Revision 25 Effective March 2013 Page 1 of 31







FOR

DETERMINATION OF METALS BY ICP-MS

APPLICABLE TO METHODS:

EPA Method 200.8

EPA SW-846 Method 6020 and 6020A

(GL-MA-E-014 REVISION 25)



Laboratories, LLC (GEL). No contents of this document may be reproduced or otherwise

used for the benefit of others except by express written permission of GEL.

30-Sep-2013







TABLE OF CONTENTS

1.0 STANDARD OPERATING PROCEDURE FOR DETERMINATION OF METALS BY

ICP-MS................................................................................................................................. 3

2.0 METHOD CODES ............................................................................................................... 3

3.0 METHOD OBJECTIVE AND PURPOSE........................................................................... 3

4.0 METHOD APPLICABILITY AND METHOD SUMMARY.............................................. 3

5.0 METHOD SCOPE AND PERFORMANCE CHARACTERISTICS .................................. 4

6.0 DEFINITIONS...................................................................................................................... 4

7.0 INTERFERENCES TO THE METHOD.............................................................................. 7

8.0 SAFETY PRECAUTIONS AND HAZARD WARNINGS ................................................. 8

9.0 CAUTION WARNINGS ...................................................................................................... 9

10.0 APPARATUS, MATERIALS, REAGENTS, EQUIPMENT, AND INSTRUMENTS..... 10

11.0 SAMPLE HANDLING AND PRESERVATION REQUIREMENTS............................... 11

12.0 SAMPLE PREPARATION TECHNIQUES ...................................................................... 11


14.0 PREPARATION OF STANDARD SOLUTION AND QUALITY CONTROL

SAMPLES .......................................................................................................................... 12

15.0 INSTRUMENT CALIBRATION ....................................................................................... 12

16.0 INSTRUMENT PERFORMANCE REQUIREMENTS .................................................... 13

17.0 ANALYST AND METHOD VERIFICATION REQUIREMENTS.................................. 14

18.0 ANALYSIS PROCEDURES AND INSTRUMENTAL OPERATION............................. 14

19.0 CALCULATIONS AND DATA REDUCTION METHODS ............................................ 17

20.0 DATA RECORDING ......................................................................................................... 18

21.0 QUALITY CONTROL REQUIREMENTS ....................................................................... 18

22.0 DATA REVIEW, VALIDATION, AND APPROVAL PROCEDURES........................... 22

23.0 DATA REPORTING .......................................................................................................... 24

24.0 RECORDS MANAGEMENT AND DOCUMENT CONTROL ....................................... 24

25.0 LABORATORY WASTE HANDLING AND DISPOSAL: SAMPLES, EXTRACTS,

DIGESTATES, AND REAGENTS ................................................................................... 25

26.0 REFERENCES ................................................................................................................... 25

27.0 HISTORY ........................................................................................................................... 27

APPENDIX 1: FREQUENCY OF QUALITY CONTROL ACTIVITIES.................................. 27

APPENDIX 2: ACCEPTANCE LIMITS .................................................................................... 28

APPENDIX 3: INTERNAL STANDARDS WITH ASSOCIATED ANALYTES/ISOTOPES . 30

APPENDIX 4: RADIOCHEMISTRY CONVERSION CALCULATIONS FOR URANIUM

ISOTOPES.......................................................................................................... 31

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1.0 STANDARD OPERATING PROCEDURE FOR DETERMINATION OF METALS BY ICP-

MS

2.0 METHOD CODES

2.1 EPA SW-846 Method 6020

2.2 EPA SW-846 Method 6020A

2.3 EPA Method 200.8

2.4 ASTM D4698-92 Total Dissolution

3.0 METHOD OBJECTIVE AND PURPOSE

This standard operating procedure (SOP) describes the determination of metals using a

Perkin Elmer ELAN ICP-MS Model 6100 Spectrometer or a Perkin Elmer ICP-MS Model

9000 Spectrometer. Prior to analysis, samples must be digested using appropriate sample

preparation methods (such as Methods 3005, 3010, 3050, or 200.2) and other applicable

requests.

4.0 METHOD APPLICABILITY AND METHOD SUMMARY

4.1 Refer to Appendix 3 for analyte lists and masses.

4.2 Applicable Matrices: These methods are applicable to the determinations of any of

the analytes listed above for various matrices including waters, oils, soils, sludges,

biological tissues, Toxicity Characteristic Leaching Procedure (TCLP) extracts and

other more unusual types of sample which are generally classified as a

miscellaneous matrix.

4.3 General Method Summary: After the samples are prepared in accordance with the

sample preparation SOP, they are analyzed by Inductively Coupled Plasma-Mass

Spectrometry (ICP-MS) as follows:

4.3.1 The instrument is calibrated with a minimum of two calibration points for

each element to be analyzed. The points consist of a calibration blank

solution to define the lower calibration point and at least one standard

calibration solution at the analyte concentrations to define the higher

calibration point(s). A correlation coefficient of 0.995 or better (0.998 or

better for SW-846 Method 6020A) is required for each analyte if multiple

standards are used or the instrument is recalibrated for the analyte of

interest.

4.3.2 Prepared client samples and numerous check standards and quality control

samples, identified in Section 22.1 are then analyzed. The check standards

and quality control samples are used to determine the quality and

acceptability of the analytical data.

4.3.3 Continuing Calibration Verification standards (CCV) and Continuing

Calibration Blanks (CCB) are analyzed a minimum of every 10 samples to

ensure that the instrument is continuing to perform correctly. For 6020A,

low level continuing calibration verification standards are analyzed in

conjunction with the CCVs and CCBs.

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4.4 Method Codes: Analyses must conform to SW-846 Method 6020, SW-846 Method

6020A, EPA Method 200.8, and/or customer contract specifications.

4.5 Radiochemistry conversion calculations for the uranium isotopes are included in

Appendix 4.

5.0 METHOD SCOPE AND PERFORMANCE CHARACTERISTICS

5.1 Calibration Range: The range of concentrations between the calibration blank,

typically 0, and that of the highest calibration standard for each analyte. Calibration

standards vary according to method and equipment. A minimum of two, a blank

and value standard, are required.

5.2 Linear Dynamic Range standards (LRS) are analyzed with each calibration. The

linear calibration range that may be used for the analysis of samples should be

judged by the analyst from the resulting data. The instrument is calibrated. The

target linear range should be prepared and analyzed. The LRS results must fall

within ± 10% of the target value. This LRS value is entered into the instrument’s

software. Any hits below this value will be valid. Hits at or above this value will

be flagged by the system and must be diluted to fall within the linear dynamic range.

If a linear range standard is not used for a specific calibration, the highest

calibration standard becomes the upper limit of reporting.

5.3 Instrument Detection Limits (IDLs) in µg/L are determined by calculating the

average of the standard deviation of the three runs on three non-consecutive days

from the analysis of a reagent blank solution with seven consecutive measurements

per day. Each measurement must be performed as though it were a separate

analytical sample (i.e., each measurement must be followed by a rinse and/or any

other procedure normally performed between the analysis of separate samples).

IDLs must be determined at least every three months.

5.4 Method Detection Limit (MDL) studies for each analyte are performed and/or

verified at least annually. These studies are conducted and calculated in accordance

with SW-846, Chapter 1, paragraph 5.0, and GL-LB-E-001 for the Determination of

Method Detection Limits. The relevant quantitation limits are established based on

the most current MDL study. The current MDLs are maintained and can be found

in the AlphaLIMS database.

5.5 Method Precision: To assure analytical precision of methods used, Laboratory

Control Samples (LCS) are analyzed with each batch. LCS duplicates are analyzed

with each batch when requested.

5.6 Method Bias (Accuracy) is determined by calculating recoveries of LCS of a similar

matrix.

5.7 If uncertainty and total propagated uncertainty measurements are needed, they may

be determined using GL-QS-E-014 for Quality Assurance Measurement

Calculations and Processes.

6.0 DEFINITIONS

6.1 AlphaLIMS: The Laboratory Information Management System used at GEL

Laboratories, LLC.

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6.2 Analysis Date/Time: The date and military time (24-hour clock) of the introduction

of the sample, standard, or blank into the analysis system.

6.3 Analytical Sample: Any solution of media introduced into an instrument on which

an analysis is performed excluding instrument calibration, initial calibration

verification (ICV), initial calibration blank (ICB), continuing calibration verification

(CCV), and continuing calibration blank (CCB).

6.4 Calibration Standard (CAL): A solution prepared from the primary dilution

standard solution or stock standard solutions and the internal standards surrogate

analytes. The CAL solutions are used to calibrate the instrument response with

respect to analyte concentration.

6.5 Continuing Calibration Blank (CCB): An aliquot of reagent water or other blank

matrix that is analyzed after each CCV. The CCB is used to determine whether the

analytical sequence is in control during sample analysis.

6.6 Continuing Calibration Verification (CCV) Standard: An aliquot of reagent water

or other blank matrix to which known quantities of the method analytes are added.

The CCV is analyzed exactly like a sample, periodically throughout the run

sequence. Its purpose is to determine whether the analytical sequence is in control

during the sample analysis. It may be prepared from the same source as the

calibration standards, and is usually of varied concentrations.

6.7 Contract Required Detection Limit (CRDL): Minimum level of detection

acceptable under the client project requirements.

6.8 Control Limits: A range within which specified measurement results must fall to be

compliant. Control limits may be mandatory, requiring corrective action if

exceeded, or advisory, requiring that noncompliant data be flagged.

6.9 Correlation Coefficient: A number (r) that indicates the degree of dependence

between two variables (concentration-absorbance). The more dependent they are,

the closer the value to one. Determined on the basis of the least squares line.

6.10 Data Qualifiers: The following qualifiers should be used in order to identify

analytical situations that might need additional information stated in narrative

before the release of the data.

U - Non-Detect. Below the Instrument or Method Detection Limit (depending

upon specific project requirements)

B - Sample concentration value is between the MDL (or IDL) and the CRDL or

analyte was detected in the Method Blank (Client Specific)

J - Sample concentration is between the MDL (or IDL) and the CRDL-client

specific qualifier.

Blank - Concentration value is above the CRDL

* - An RPD value in the duplicate sample is out of criteria

N - A percent recovery value in the spike sample is out of criteria

E - A percent difference in the serial dilution sample is out of criteria because

of the presence interference.

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6.11 Duplicate: A second aliquot of a sample that is treated the same as the original

sample in order to determine the precision of the method.

6.12 Initial Calibration Blank (ICB): An aliquot of reagent water or other blank matrix

that is analyzed after each ICV. The ICB is used to determine whether there is

carryover contamination.

6.13 Initial Calibration Verification (ICV): A solution of method analytes of known

concentrations. The ICV is obtained from a source external to the laboratory and

different from the source of calibration standards. It is used to check laboratory

performance with externally prepared test materials.

6.14 Instrument Performance Check Solution (IPC): A solution of one or more method

analytes, surrogates, internal standards, or other test substances used to evaluate the

performance of the instrument system with respect to a defined set of criteria.

6.15 Interferants: Substances that affect the analysis for the element of interest.

6.16 Internal Standard: Pure analyte(s) added to a sample, extract, or standard solution

in known amounts and used to measure the relative responses of other method

analytes.

6.17 Laboratory Control Standard (LCS): An aliquot of reagent water or other blank

matrix to which known quantities of the method analytes are added in the

laboratory. The LCS is analyzed exactly like a sample, and its purpose is to

determine whether the methodology is in control and whether the laboratory is

capable of making accurate and precise measurements.

6.18 Linear Calibration Range (LCR): The concentration range over which the

instrument response is linear.

6.19 Method Blank (MB): An aliquot of reagent water or other blank matrix that is

treated exactly as a sample including exposure to all glassware, equipment, solvents,

reagents, internal standards, and surrogates that are used with other samples. The

MB is used to determine if method analytes or other interferences are present in the

laboratory environment, the reagents, or the apparatus.

6.20 Method Detection Limit (MDL): The minimum concentration of an analyte that can

be identified measured and reported with 99% confidence that the analyte

concentration is greater than zero.

6.21 Serial Dilution: The dilution of a sample by a known factor. When corrected by the

dilution factor, the diluted sample should agree with the original undiluted sample

within the specified limits. Serial dilution may reflect the influence of interferants.

6.22 Spike (Matrix Spike or Post Spike): An aliquot of an environmental sample to

which known quantities of the method analytes are added in the laboratory. The MS

or PS is analyzed exactly like a sample, and its purpose is to determine whether the

sample matrix contributes bias to the analytical results. The background

concentrations of the analytes in the sample matrix must be determined in a separate

aliquot and the measured values in the MS or PS corrected for background

concentrations.

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6.23 Limit of Detection (LOD): An analyte, method and matrix specific estimate of the

minimum amount of a substance that can be reliably detected.GEL has established

LOD = 2 x MDL.

6.24 Limit of Quantitation (LOQ): An analyte, method and matrix specific estimate of

the minimum amount of a substance that can be reported with a specific level of

confidence. The LOQ is set at or above the concentration of the lowest initial

calibration standard. The laboratory must empirically demonstrate precision and

bias at the LOQ. The LOQ and associated precision and bias must meet client

requirements and must be reported. GEL uses the following guidance (LOD <

LOQ):

When LOD < PQL, PQL = LOQ

When LOD > PQL, LOQ is raised to next lowest calibration standard.

6.25 Practical Quantitation Limit (PQL): The PQL is typically at or above the lowest

point on an acceptable initial calibration curve. It may also be determined by

multiplying the MDL by approximately 2 to 10. Concentrations of a target analyte

determined to be greater than its PQL are defined as quantitative results. This limit

is not used in DoD ELAP reporting.

6.26 Statistical Process Control (SPC) Limits: Statistically derived limits that establish

acceptable ranges for recoveries of analytes of interest, including LCS, MS, MSD,

PS and PSD.

6.27 Stock Standard Solution: A concentrated solution containing one or more method

analytes prepared in the laboratory using certified reference materials or purchased

from a reputable commercial source.

6.28 10% Frequency: A frequency specification during an analytical sequence allowing

for not more than 10 analytical samples between required calibration verification

measurement, as specified by the EPA methodology.

7.0 INTERFERENCES TO THE METHOD

7.1 Chemical interferences are minimal in ICP-MS Spectroscopy because the extremely

high energy of the plasma breaks nearly all the chemical bonds. However, ICP-MS

analysis is subject to the following three types of interferences:

7.1.1 Physical interferences are those physical properties of a sample solution

that prevent their introduction to the plasma with efficiency equal to that of

the calibration standards. This type of interference can be corrected via the

bias correction calculation in SW-846, Chapter 1, paragraph 5.0, through

the use of an internal standard in accordance with the instrument operating

manual or by diluting the sample in reagent blank solution until the percent

recovery falls with method guidelines.

7.1.2 Isobaric elemental interferences are caused by isotopes of different

elements that form singly or doubly charged ions of the same nominal

mass-to-charge ratio and that cannot be resolved by the mass spectrometer.

If analytical isotopes are selected that may have an isobaric interference,

then all data obtained under such conditions must be corrected by

30-Sep-2013







measuring the signal from another isotope of the interfering element and

subtracting the appropriate signal ratio from the isotope of interest.

7.1.3 Isobaric polyatomic ion interferences are caused by ions consisting of more

than one atom that have the same nominal mass-to-charge ratio as the

isotope of interest, and that cannot be resolved by the mass spectrometer in

use. These ions are commonly formed in the plasma or interface system

from support gases or sample components. Most of the common

interferences have been identified and are listed in Method 200.8, Table 2

together with the method elements affected. Such interferences must be

recognized, and when they cannot be avoided by the selection of

alternative analytical isotopes or sample prep procedures, appropriate

corrections must be made to the data.

8.0 SAFETY PRECAUTIONS AND HAZARD WARNINGS

8.1 PREVENT SKIN AND EYE CONTACT BY USING SPECIFIED PERSONAL

PROTECTIVE EQUIPMENT WHEN MAKING STOCK REAGENTS.

8.2 WORK UNDER A HOOD TO PREVENT INHALATION WHEN MAKING

STOCK REAGENTS.

8.3 Sample digestates are not extremely volatile or spontaneously combustible, but they

are normally acidic and should be handled with care. Small spills may generally be

wiped up with paper towels that can be disposed of in the trash. Larger spills may

require the use of a mop, and the mop head may have to be disposed of as

potentially hazardous waste in accordance with the Laboratory Waste Management

Plan (GL-LB-G-001). If the spilled digestates begin any obvious fuming or

reacting, pour a generous amount of the acid neutralizer, which is located in each

lab, onto the spill before attempting to clean it up.

8.3.1 Gloves should be worn to avoid skin contact with digestate during clean-

up.

8.3.2 Eye protection is required when handling samples and an eyewash station

is located in each analysis lab.

8.3.3 Do not persist in cleaning up a spill in the presence of strong fumes. Move

out of the area, try to isolate the area and notify your supervisor

immediately.

8.4 Handling radioactive samples requires the use of gloves, a lab coat or an apron in

addition to eye protection. Refer to GL-RAD-S-004 for Radioactive Material

Handling

8.5 These instruments use high voltage electricity and therefore, should be shut

completely down any time electronic components may be exposed to personnel or

any liquids.

8.6 Wear eye protection with side shields while performing procedures in the lab.

8.7 All chemicals and samples should be treated as potential health hazards, and

exposure to these chemicals must be reduced to the lowest level possible. GEL

maintains a current awareness file of Occupational Safety and Health

Administration (OSHA) regulations regarding the safe handling of the chemicals in

30-Sep-2013







the laboratory as well as a reference file of Material Safety Data Sheets (MSDS).

These documents are maintained in the laboratory. Individual sample MSDS forms

provided by the clients are kept in Login.

8.8 Personal protective equipment

8.8.1 Gloves are required when handling the chemicals in this procedure.

8.8.2 Work under a hood when using concentrated acids.

8.9 Prior to handling radioactive samples, analysts must have had radiation safety

training and must understand their full responsibilities in radioactive sample

handling. Some general guidelines follow:

8.9.1 Wear a lab coat when working with radioactive samples.

8.9.2 Prohibit admittance to immediate work area.

8.9.3 Protect counter tops with counter paper or work from radioactive sample

handling trays.

8.9.4 Post signs indicating radioactive samples are in the area.

8.9.5 Take swipes of the counter tops upon completion of work. Deliver those

swipes to the nearest swipe count box.

8.9.6 Segregate radioactive wastes. Radioactive waste containers are obtained

from Waste Management.

8.10 All samples, chemicals, extracts, and extraction residues must be transferred,

delivered, and disposed of safely according to all related SOPs.

8.10.1 Segregate solid wastes from liquid wastes in the satellite area containers.

8.10.2 Segregate oil wastes from water-soluble wastes in the satellite area

containers

8.11 Never leave gas cylinders unchained or untied, including when they are on the

moving carts.

8.12 In the event of an accident or medical emergency, call for help immediately. When

time and safety permit, an accident report form should be completed and turned in

to the safety committee.

8.13 Fire escape routes are posted in the lab; all personnel should be familiar with them.

In addition, fire safety equipment such as fire extinguishers is located in the lab.

Training is available on the proper operation of this equipment.

9.0 CAUTION WARNINGS

9.1 Because they can be health hazards, the exhaust gases from the plasma and vacuum

systems must be eliminated through the laboratory's ventilation duct, which is

attached to the instrument's exhaust vent. If inadequate ventilation occurs, pump-

fluid vapor, ozone, and other toxic products of combustion can accumulate in the

laboratory and cause bodily harm. Hydrofluoric acid (HF) fumes, if inhaled,

extensively burn lung tissue. Ensure that the exhaust system established at

installation continues to operate effectively.

9.2 Prepare sample and transfer acids using a hood to avoid fumes.

9.3 Store and prepare sample away from the instrument to minimize corrosion.

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9.4 Clean up any spills quickly.

9.5 The drain vessel contains the spray chamber's effluent, which can be toxic.

Corrosion of the vessel and connecting tube can result in leaks that damage the

instrument or cause bodily harm.

9.5.1 Use the capped plastic drain vessel that was provided with the instrument.

Never use glass.

9.5.2 Place the drain vessel on the instrument table below the peristaltic pump

where the container is easy to check.

9.5.3 Check the drain vessel frequently. Empty it before it is three-fourths full.

9.5.4 Check the tubing and vessel for deterioration. If the tubing becomes brittle

or cracked, replace it. Organic solvents cause more rapid deterioration

than aqueous solutions.

9.6 The torch and interface remain hot after the plasma is turned off. Do not touch the

torch box or interface cones for 10 minutes after the plasma has been shut off.

9.7 High voltages and radio frequencies are potential hazards of the ICP-MS. Shut the

instrument down completely before removing any of the outside panels (to clean air

filters, replace a fuse, etc.).

9.8 When changing the rotary pump oil, remember that the pump oil may be hot. The

oil can cause a burn if allowed to contact the skin.

10.0 APPARATUS, MATERIALS, REAGENTS, EQUIPMENT, AND INSTRUMENTS


10.1.1 Replacement special glass parts for the ICP-MS such as quartz torch

bodies, injector tips and spray chambers may be ordered from a qualified

vendor through the GEL Purchasing Agent.

10.1.2 Replacement ICP-MS interface parts such as sampling cones, skimmer

cones and ion-optics can be purchased from a qualified vendor through the

GEL Purchasing Agent.

10.1.3 Consumable materials such as tubing are often attainable from various

scientific product companies. The GEL Purchasing Agent can help to find

the best prices. These items may also be ordered from the instrument

manufacturer if necessary. All orders must be placed through the GEL

Purchasing Agent.

10.2 Reagents, Chemicals, and Standards

10.2.1 Reagents: Refer to Reagent Logbook

10.2.2 Standards: Refer to GL-LB-E-007 for Laboratory Standards

Documentation and GL-LB-E-015 for Control of Laboratory Standards.

10.2.3 Other Chemicals: Additional compounds, surfactants, oils, cleaning

agents, etc., may be routinely ordered through the GEL Purchasing Agent.

10.3 Instrumentation

10.3.1 Perkin Elmer ICPMS ELAN Model 6100 with IBM compatible PC,

Monitor, Printer.

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10.3.2 Perkin Elmer ICP-MS ELAN Model 9000 with IBM compatible PC

Monitor, Printer.

10.3.3 CETAC Model ASX-500 Autosampler (PE 6100)

10.3.4 CETAC Model ASX-510 Autosampler with accessory autodiluter (PE

9000)

10.3.5 Neslab CFT75 recirculating bath provides cooling to the ICP-MS (PE

6100/ PE 9000)

10.3.6 CETAC ASXpress Rapid Sample Introduction System

11.0 SAMPLE HANDLING AND PRESERVATION REQUIREMENTS

11.1 Aqueous samples should be preserved with nitric acid to a pH of < 2 prior to receipt

by the analyst. Solid samples should be kept at 0° < 6° C prior to digestion.

11.2 Refer to GL-SR-E-001 for Sample Receipt, Login and Storage.

12.0 SAMPLE PREPARATION TECHNIQUES

12.1 All samples except drinking water with Turbidity < 1 NTU and samples specifically

exempted by contract, are prepared in accordance with the following SOPs:

12.1.1 GL-MA-E-016 for Sample Preparation for Total Recoverable Elements by

EPA Method 200.2 (USEPA Method 200.2)

12.1.2 GL-MA-E-006 for Acid Digestion of Total Recoverable or Dissolved

Metals in Surface and Groundwater Samples for Analysis by ICP or ICP-

MS (USEPA SW-846 Method 3005A)

12.1.3 GL-MA-E-008 for Acid Digestion of Total Metals in Aqueous Samples

and Extracts for Analysis by ICP or ICP-MS (USEPA SW-846 Method

3010A)

12.1.4 GL-MA-E-009 for Acid Digestion of Sediments, Sludges and Soils

(USEPA SW-846 Method 3050B)

12.1.5 GL-MA-E-021 for Total Digestion of Sediment Samples for Analysis by

ICP or ICP-MS (ASTM D4698-92)

12.2 Additional filtration may be required to prevent clogging of sample introduction

system.

12.3 All sample preparation records are stored in AlphaLIMS.

12.4 Sample spills should be handled as stated in Section 8.3.


13.1 Routine Preventative and Special Operational (Failure)

13.2 Routine Preventative Maintenance (PM) Procedures are done as follows:

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13.3 Non-Routine Maintenance Procedures (Special, Operational or Failure Mode

Maintenance)

13.3.1 If the instrument will not function properly see the trouble shooting section

in the appropriate Maintenance Manual.

13.3.2 If the analyst is unable to determine cause/fix instrument, the GEL Service

Engineer is called, and if needed, the manufacturer’s customer support

number may be found in the owner’s maintenance manuals.

13.4 Refer to ICP-MS Maintenance Logbook for routine records. Service call records

are also available.

14.0 PREPARATION OF STANDARD SOLUTION AND QUALITY CONTROL SAMPLES

14.1 Source standards records are recorded in AlphaLIMS.

14.2 Recommended Suppliers: Refer to source log and use Approved Vendors List

maintained in Procurement.

14.3 Standards are receipted, labeled, prepared and stored in accordance with the GL-

LB-E-007 for Laboratory Standards Documentation.

15.0 INSTRUMENT CALIBRATION

15.1 Samples may be analyzed manually or automatically.

15.1.1 Tuning for each instrument is performed daily according to the following

directions and criteria.

15.1.2 PE 6100/ 9000: Aspirate a tuning solution consisting of 10 µg/L each of 9Be,

24Mg,

59Co,

115In and

208Pb. Perform 5 replicates. Manufacturer's

recommended tune criteria are as follows:

Frequency Procedure

When Needed Clean nebulizer tip after use.

Replace peripump sample introduction tubing.

Change pump hoses on drain systems.

Check drain waste collection containers, and empty as necessary.

Check Neslab water level and add water if required.

Clean/replace interface cones.

Clean/replace nebulizer.

Clean/replace torch.

Check/replace water filter.

Quarterly Change oil in interface rotary pump (or as needed).

Clean ion lenses 4-6 months (or as needed).

6 Months Clean air filters.

12 months Change pump oil in backing rotary pump.

Evaluate/replace EM (electron multiplier)

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Parameter Starting Point 9Be ± 0.10 amu

24Mg ± 0.10 amu

59Co ± 0.10 amu

115In ± 0.10 amu

208Pb ± 0.10 amu

Ba++

net intensity mean < 0.05 or 5%

CeO net intensity mean < 0.03 or 3%

Be, Mg, Co, In, Pb net intensity RSD

< 5%

Resolution at 10% peak height

< 0.9 amu

15.1.3 Conduct additional tuning procedures as specified by client contract or

other methodology.

15.1.4 If any of the preceding tune criteria does not meet the recommended

requirements, investigate the problem, correct the situation, and reanalyze

the tune sequence.

15.1.5 Standardization: Standardization is required on a daily basis.

15.2 Internal standards are used as appropriate for the analytes of interest. The internal

standards are made in the appropriate acid and contain varying concentrations of

such elements as 45

Sc, 74

Ge, 115

In, 175

Lu, and/or 181

Ta. The internal standard

solution is mixed in-line with the sample stream using a dedicated channel of the

peristaltic pump. Internal standards may be added at the time of analysis as an

alternative to in-line mixing. Alternate internal standards may be used to meet

client needs.

15.3 Calculations are described in the instrument manual.

15.4 Calibration standards vary according to method and equipment. A minimum of

two, a blank and value standard, is required.

15.5 For required quality control standards refer to Section 21.0.

15.6 For continuing calibration requirements refer to Section 21.0.

15.7 For what to do when initial or continuing calibrations fail to meet requirements,

refer to Section 21.0.

16.0 INSTRUMENT PERFORMANCE REQUIREMENTS

16.1 Before samples may be analyzed to generate reportable data, the instrument must

have been tuned and calibrated. Also, the Initial Calibration Verification (ICV),

which is prepared from an independent source, Initial Calibration Blank (ICB), the

Reportable Detection Limit (CRDL), the Interference Check Standards (ICS-A,

ICS-AB), and the Linear Range Standards (LRS) must meet the requirements stated

in Section 21.2 for each analyte being reported, unless otherwise required by

methodology, clients or contracts.

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16.2 The instrument calibration and all continuing verification data is maintained in the

printed hard copy file. The printouts are kept in chronological order by instrument.

Recent files are in the metals laboratory; older records are archived in short or long-

term storage.

17.0 ANALYST AND METHOD VERIFICATION REQUIREMENTS

17.1 Analyst training is conducted and certified in accordance with the GL-HR-E-002 for

Employee Training.

17.2 Method performance is verified by the conductance of MDL studies in accordance

with GL-LB-E-001 for The Determination of Method Detection Limits, and by the

evaluation of LCS and LCS duplicates for each batch of samples.

18.0 ANALYSIS PROCEDURES AND INSTRUMENTAL OPERATION

18.1 All samples are introduced in a set measured quantity, via a peristaltic pump,

through a nebulizer into a spray chamber and carried with argon gas through the

Radio Frequency (RF) field to generate analyte ions that are selected and measured

by the quadruple mass spectrometer.

18.2 Run Sequence

18.2.1 Instrument Calibration executed in accordance with Section 16.

18.2.2 Initial Calibration Verification steps include:

18.2.2.1 ICV

18.2.2.2 ICB

18.2.2.3 CRDL (low level ICV for 6020A)

18.2.2.4 ICS-A

18.2.2.5 ICS-AB

18.2.2.6 CCV

18.2.2.7 CCB

18.2.2.8 LRS

18.2.2.9 CCV

18.2.2.10 CCB

18.2.3 Sample Run (10 samples or less)

18.2.4 Continuing Calibration Verification:

18.2.4.1 CCV

18.2.4.2 CRDL (for SW-846 Method 6020A only and analyzed at end of

batch).

18.2.4.3 CCB

18.2.5 Repeat steps 18.2.3 and 18.2.4 until end of run or verification is out of

specification. When the latter occurs, repeat step 18.2.1 and continue with

steps 18.2.2 and 18.2.3.

18.2.6 Repeat steps 18.2.3 through 18.2.5 until the end of the run or verification is

out of specification. When latter condition occurs, repeat 18.2.1 and

continue sequentially through 18.2.7.

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18.2.7 Final Verification Steps

18.2.7.1 ICS-A (if required)

18.2.7.2 ICS-AB (if required)

18.2.7.3 CCV

18.2.7.4 CRDL (for SW-846 Method 6020A only)

18.2.7.5 CCB

NOTE: Method 6020A only requires there to be a closing low level

continuing calibration standard (CRDL). For ease of analysis, the CRDL

standard can be analyzed every 10 samples.

18.3 For data storage refer to Section 24.1.

18.4 General operation of the instrument.

18.4.1 The Perkin Elmer Model 6100 and Perkin-Elmer Model 9000 are

inductively-coupled argon plasma mass spectrometers. The ICP-MS is

capable of determining analytes from m/z = 6 (Li) through m/z = 238 (U).

The operating software of the system is based on Microsoft Windows.

18.4.2 Set-up

18.4.2.1 Attach the nebulizer argon line to the quick-connect on the

nebulizer’s argon tube and ensure that it is tightly in place.

18.4.2.2 Attach the nebulizer and endcap to the spray chamber.

18.4.2.3 Attach sample pump tubing to the front peristaltic pump

(various sizes may be used depending on need), and attach feed

end to endcap.

18.4.2.4 If running manually, place the suction end of the sample tubing

in acidified rinse water; otherwise attach it to the autosampler.

18.4.2.5 Ensure that drain hose is connected to the spray chamber and

properly plumbed through the drain peristaltic pump.

18.4.3 Run Procedure

18.4.3.1 Refer to the respective owner’s manuals for specific

instructions for tuning, sequence loading, and method

development on each instrument; ELAN 6000/6100 software

guide; ELAN 9000 software guide.

18.4.3.2 The owner’s manual for each instrument is located in the ICP-

MS laboratory.

18.4.4 Typical Analysis Problems

18.4.4.1 Sample Overrange: If a requested element is overrange for a

sample, it is necessary to dilute the sample and rerun. Dilution

factors must be taken into account when reporting final values.

18.4.4.2 Interferences: Although the ICP-MS can compensate for many

interferences with appropriate correction factors, unpredicted

interferences may still occur. If the analyst suspects this, then

30-Sep-2013







the sample should be diluted and rerun. Dilution factors must

be taken into account when reporting final values.

18.4.4.3 Torch/Sample Introduction Drift: Various changes in torch

plasma conditions or sample introduction can have a great

effect on the detector counts. They must be corrected or the

instrument must be re-standardized.

18.4.4.3.1 If oils or solid samples have been run, and the CCV

is not acceptable, allow the instrument to rinse 15 to

20 minutes. If CCV is then acceptable, reanalyze

the samples and continue. If the CCV again fails its

requirements, re-standardize as necessary.

18.4.4.3.2 If sample introduction drift is suspected, check

peristaltic pump tubing for collapse and replace as

needed.

18.4.4.3.3 Tubing connections may become loose allowing air

to bubble into the sample path. Tighten or replace

tubing. If necessary, seal with Parafilm.

18.4.4.4 Serial dilution: If the analyte concentration is sufficiently high

(minimally, a factor of 100 times above the IDL for non-DOE

Clients, 100 x the MDL for DOE-Alb Clients, and 50 times the

LOQ for DoD QSM in the original sample), an analysis of a

five fold (1 + 4) dilution should agree within 10% of the

original determination. If not, a chemical or physical

interference effect should be suspected.

18.5 Power switches and auxiliaries

18.5.1 Each instrument has one main power switch. Refer to the respective

maintenance manuals for the location (ELAN 6100 and ELAN 9000

Hardware Guide). This switch remains on except while servicing the

instrument.

18.5.2 The computer system has 3 power cords all connected to a switchable

power strip: the computer main, the monitor and the printer power cords.

The power to these is left on while the instrument is not in use for short

times (e.g. overnight).

18.5.2.1 The main computer switch is on the front of the CPU.

18.5.2.2 The monitor switch is on the front of the monitor itself.

NOTE: If the computer is left in use without an analyst present for an

extended period of time, turn the monitor off to prevent screen burn-in.

18.5.2.3 The printer switch is on the lower front of the printer. Refer to

printer manual for operating instructions.

18.5.3 Argon gas is provided through a manifold from the storage tank. Under

normal conditions a constant argon flow is available.

18.5.4 Start-up

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18.5.4.1 Before starting, ensure that the power is on and the vacuum

system is switched on.

18.5.4.2 The owner’s manual for each instrument provides specific

instructions for ignition of the plasma (refer to Section 18.5.1

for software manuals).

18.5.4.3 The plasma should be steady and should not flicker.

18.5.4.4 Once ignition has occurred, levels may be adjusted; it is best to

set levels appropriate to the method by loading or editing an

appropriate tune file and allow 30 minutes for warm-up.

18.5.5 Shutdown

18.5.5.1 When the plasma is off, the instrument is either in Standby or

Shutdown mode. The ICP-MS should be completely shut down

only in case of major maintenance, relocation of the instrument,

or when the lab is closed for an extended time.

18.5.5.2 Daily shutdown (if required): Refer to the respective owner’s

manual shutdown procedures (Refer to Section 18.5.1 for

software manuals.)

18.6 Sample quantity requirements are approximately 5 mL for each run with the

nebulizer. If out of specification or range, further sample may be necessary for

reruns.

18.7 The autosampler can be used by attaching introduction tube to sample introduction

system, and rinsing tubing to peristaltic pump and following autosampler table set-

up and procedures. To define a sequence, refer to the appropriate software manual

(refer to Section 18.5.1).

19.0 CALCULATIONS AND DATA REDUCTION METHODS

19.1 Any dilutions, concentrations, or preparation factors must be taken into account

prior to reporting data to a client.

Relative Percent Difference = 2

Value 2 SampleValue 1 (Sample

Value 2 Sample - Value 1 Sample * 100

+

Matrix Spike Recovery = PF * DF *ion ConcentratNominalSpike

PF) * DF * ValueSample - PF * DF * Value(Spike * 100

Post Spike Recovery = ionConcentratNominalSpike

Value)Sample - Value(Spike * 100

LCS Recovery = PF*DF*ion ConcentratNominal

PF) * DF * Value(Sample * 100

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Where: Sample Value = instrument reading for the sample

Spike Value = instrument reading for the spiked sample

DF = Dilution Factor

PF = Preparation Factor

Relative Error Ratio (RER) 2 sigma equation:

NOTE: Activity calculations can be found in Appendix 4 of this SOP. Two sigma

TPU calculations can be found in SOP GL-QS-E-014.

19.2 Care must be taken that the correct units are being employed.

20.0 DATA RECORDING

20.1 ICP-MS data are generally stored to the hard disk drive of the ICP-MS computer

system and printed at the instrument as each sample is analyzed.

20.2 ICP-MS samples are generally analyzed in three replicates (minimum of 2) and the

reported value is the average of the replicates. The data for individual replicates is

stored in the computer.

20.3 Data are processed locally by manual or programmable procedures to eliminate

unused data, to enter dilution factors, and to enter relevant conversion factors prior

to uploading to AlphaLIMS.

21.0 QUALITY CONTROL REQUIREMENTS

21.1 Frequency of Quality Control Activities (also refer to Appendix 1)

21.1.1 Initial Calibration Verification (ICV) is performed immediately following

each calibration and Continuing Calibration Verification (CCV) is

performed after at least every 10 samples.

21.1.2 Initial Calibration Blank (ICB) is performed immediately following the

ICV and Continuing Calibration Blanks (CCB) must run with each CCV.

21.1.3 An Interference Check Standard (ICS) is analyzed at the beginning of each

analytical run and at least once every twelve hours (if required). Additional

requirements may be specified by client contract or methodology.

21.1.4 The PQL standard is analyzed after each calibration and recommended at

least every 10 samples between the CCV and CCB analyses for SW-846

Method 6020A. Method 6020A requires analysis at the end of every batch

and only recommends analysis every 10 samples. This standard may also

be labeled as a CRDL standard.

21.1.5 A method blank (MB) is performed for each batch of 20 or fewer samples

or per client requirement.

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21.1.6 A matrix spike (MS) and a duplicate (DUP), or matrix spike (MS) and

matrix spike duplicate (MSD) are analyzed for each batch of 20 or fewer

samples or per client requirements (5% frequency). For EPA 200.8, the

same QC are analyzed for each batch of 10 or fewer samples (10%

frequency).

21.1.7 A laboratory control sample (LCS) is analyzed with each batch of 20 or

fewer samples. An LCS duplicate (LCS DUP) may be added if required by

the client.

21.1.8 Serial dilutions or analytical spikes are analyzed to confirm the presence or

absence of interferences when analyzing a new matrix type. The serial

dilution is generally performed at a 5x of the test sample.

21.1.9 A post spike (PS) is required for DoD-QSM or SW 846 6020A if the

matrix spike (MS) or matrix spike duplicate (MSD) recoveries fall outside

of the limits in section 21.2.8. Post spikes can also be performed at client

request.

21.2 Acceptance Limits (also refer to Appendix 2)

21.2.1 ICV results must be between 90% and 110% of the true values for work

under EPA SW-846 Method 6020A or EPA Method 200.8. CCV results

must be between 90% and 110% of the true values for work under EPA

Method 200.8 or SW846 Method 6020A.

NOTE: The ICV is the second source standard and may be used as the CCV as it

also will show calibration verification.

21.2.2 ICB and CCB results must have an absolute value less than the Reporting

Limit (RL). For DoD QSM analysis, the absolute value must be less than

the LOD. If this is not the case, the reason for the out-of-control condition

must be found and corrected, or any data reported must be 10 times greater

than the absolute value for the element or less than the RL.

21.2.3 Interference Check Sample results must be monitored at the beginning of an

analytical run or once every 12 hours, whichever is more frequent, for work

under SW-846. The ISCA and ICSAB must recover 80-120% the reporting

level for the spiked analysis and must have an absolute value less that 2x

the reporting level for the non-spiked analyte. For DoD QSM, the ICSA

must have an absolute value of less than the absolute value of the LOD

analytes.

21.2.4 The Linear Range Standard (LRS) is analyzed within the calibration

verification read back and must fall between 90% and 110% of the true

values. Meeting these criteria allows target analyte concentration to be

reported up to the LRS concentration thus extending the calibration range

of the instrument. Any sample concentrations above the LRS

concentration will be diluted to fall below the concentration of the linear

calibration range standard.

21.2.5 The intensities of all internal standards must be monitored for every

analysis. When the intensity of any internal standard fails to fall between

30-Sep-2013







30% and 120% (or 70% and 130% for SW-846 Method 6020A) of the

intensity of that internal standard in the initial calibration then the sample

must be diluted five fold (1 + 4) and reanalyzed with the addition of

appropriate amounts of internal standards. The intensity levels of the

internal standards for the calibration blanks (ICB and CCB) and instrument

check standards (ICV and CCV) must agree within + 20% of the intensity

level of the internal standard of the original calibration solution. For work

done under EPA Method 200.8, the internal standard responses of any one

internal standard must not deviate more than 60% to 125% of the original

response in the calibration blank. Five internal standards (45

Sc, 74

Ge, 115

In, 175

Lu, and/or 181

Ta) are used to cover the mass ranges reported. Refer to

Appendix 3 for list of internal standard/ analyte associations. Other exotic

analytes may be used as needed. Refer to Section 15.2.

21.2.6 Method blank results must be lower than the PQL or less than 10% of the

determined value of all samples in the batch. When performing work

under EPA Method 200.8, if LRB (laboratory reagent blank) values are

10% or more of the analyte level determined for a sample or are 2.2 times

the analyte MDL, then fresh aliquots of the samples must be prepared and

analyzed again for the affected analytes after the source of contamination

has been corrected and acceptable LRB values have been obtained. For

DoD QSM work, the absolute value must be less than ½ RL or less than

10% of the determined value of all samples in the batch. Al, Fe, Mg, Ca,

Na, and K must be less than the RL.

21.2.7 LCS results, and LCS duplicate (if performed), must be within process

control limits as established by Statistical Process Control, manufacturer’s

certification, or method requirements.

21.2.8 Matrix spikes with recoveries between 75% and 125% suggest the absence

of interference for work under EPA Method 200.8. Matrix spikes with

recoveries between 75% and 125% suggest the absence of interference for

work under SW-846 Method 6020 and SW-846 Method 6020A. Matrix

spikes with recoveries between 80% and 120% suggest the absence of

inteferences for work under DoD QSM.

21.2.9 The relative percent difference (RPD) between a sample and a sample

duplicate should be within ± 20% if the analyte concentration in the sample

or duplicate is greater than 5 times the RL. If either the sample or

duplicate concentration is less than 5 times the RL, the results should agree

within the absolute value of the RL. Results less than the MDL or IDL are

not evaluated. The relative error ratio (RER) between a sample and a

sample duplicate should be ≤ 3%.

21.2.10 Serial dilution results that agree within 10% of the original analytical

results, if the original results are greater than 100 times the instrument

detection limit or greater than 50 times the LOQ, suggest the absence of

interference.

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21.2.11 Post spikes with recoveries between 75% and 125% under EPA Method

200.8 and SW-846 Method 6020, and between 80% and 120% under SW-

846 6020A suggest the absence of interference.

21.3 Out-of-Control Situations

21.3.1 ICV and/or CCV failure requires recalibration of the instrument and/or

preparation of new standard solutions. Samples analyzed prior to or after

calibration verifications that are not acceptable for required analytes must

be reanalyzed. An ICV or CCV that has failed may be rerun once only if

there is an attributable cause known to have affected the CCV only and not

the previous samples. Examples of an acceptable cause may be a sample

tip out of solution during analysis, an incorrectly prepared CCV, or

obvious carryover in the CCV from a very high sample immediately prior

to the CCV. If a CCV is reanalyzed, the data must be lined through,

initialed and dated, and the reason for the rerun must be documented on the

raw data. In addition, corrective action should be taken to eliminate the

cause of the initial CCV failure to prevent future occurrence.

21.3.2 ICB and CCB failure requires recalibration of the instrument and/or

calibration blank solution to be remade. The CCB is acceptable if the level

of analyte in the corresponding sample(s) is 10 times greater or less than

the PQL for the failing element. For DoD QSM work, the absolute values

must be less than the LOD or less than 10% of the determined value of all

samples in the batch.

21.3.3 ICS failure requires that the instrument be re-calibrated or the interferences

be corrected, via recalculation, of Interelement Correction Factors so that

the ICS can be read within the required limits before samples are analyzed.

ICS failure at the end of an analysis period will require that the samples’

ICSA run for the affected analyte(s) during that period to be reanalyzed.

The ICSA and ICSAB must recover 80-120% for the spiked analytes and

must have an absolute value less than 2x the reporting level for the non-

spiked analytes. For DoD QSM, the ICSA must have an absolute value of

less than the LOD for the non-spiked analytes.

21.3.4 LRS failures limit the reportable calibration range to the high standard in

the calibration curve. Any sample concentration that falls above the high

calibration standard will be diluted to fall within the calibration range.

21.3.5 Internal Standard failure requires one or more of the following: five-fold

dilution of the sample, correction of the problem, termination of analysis,

recalibration of the instrument, and/or reanalysis of the affected samples

depending on whether the failure is due to the samples or the instrumental

drift.

21.3.6 Method blank results higher than the PQL and greater than 10% of any

sample value in that batch that has concentrations above the PQL require

that batch be redigested and reanalyzed. If the method blank results are

less than -2x PQL there may be significant interference, calibration, or

contamination problems with the sample, instrument, or calibration

30-Sep-2013







standards that must be resolved before the batch can be analyzed. For DoD

QSM work, the absolute value must be less than ½ RL or less than 10% of

the determined value of all samples in the batch. Al, Fe, Ca, Mg, Na, and

K must be less than RL.

21.3.7 Matrix spikes, duplicates and spike duplicates are used only as indicators

of method effectiveness on that sample and will not be used as

acceptability criteria for the process, unless a special requirement of the

client.

21.3.8 LCS and/or LCS duplicate results outside of established acceptance limits

require the batch to be redigested and reanalyzed.

21.3.9 When analytical results suggest the presence of interference, one of the

methods listed in Section 18.4.4.2 should be employed.

21.3.10 The CRDL standard should be evaluated, but no action is required if the

results fall outside of the 70-130% advisory window. For DoD QSM, the

CRDL standard must be 80-120% of the true value or recalibration is

required. For SW-846 Method 6020A, the CRDL standard must be 70-

130% of the true value or recalibration is required. This also includes the

low level continuing calibration verification standard analyzed every 10

samples. Sample results can be evaluated for reporting if they are at least

2x the CRDL for a given analyte.

21.4 Corrective actions taken for data not conforming to the requirements in Section 21.2

are stated in Section 21.3. If these corrective actions can be taken by the analyst

prior to the acceptance of the data, then no nonconformance documentation is

required. However, if these corrective actions include redigestion of the batch or

sample, if the data have already been accepted, or if the corrective action requires an

instrument service call, then a nonconformance and/or corrective action report

should be completed. This report includes the date, person requesting the action,

sample(s) or batch(s) affected, and action requested, all provided by the requester.

The person taking the action will provide any pertinent comments, their signature,

and the date the action is completed. The disposition of the nonconformance will

then be verified by the Quality Systems specialist. These reports will be kept on

file. Refer to GL-QS-E-002 for Documentation of Nonconformance Reporting

and Dispositioning and Control of Nonconforming Items.

21.5 Analytical data are evaluated for conformance with the requirements stated in

Section 21.2 by the analyst during and/or after the analysis, but before the data are

entered into AlphaLIMS. Data may be accepted or rejected by the analyst at this

point or by the data reviewer(s) as stated in Section 22.0.

22.0 DATA REVIEW, VALIDATION, AND APPROVAL PROCEDURES

22.1 After samples are analyzed, the data must go through the review process before it

can be reported out of the lab. The analyst who performed the analysis will review

the raw data prior to uploading it into AlphaLIMS. The upload process may be

handled by the analyst or by a data entry clerk.

22.2 After the upload is complete, an AlphaLIMS data report is generated that will be

passed (along with the batch sheet, data review checklist, and the raw data) to

30-Sep-2013







another analyst for a peer review. Discrepancies found in this review will be

resolved before the batch data are passed and the status updated.

22.3 When this peer review is completed and all of the data are found to be acceptable,

the reviewer signs and dates the batch data report and updates the status of the batch

to done. If the reviewer determines that the reviewed data are not acceptable and

requires additional work or correction, data are returned to the analyst or

representative with an appropriate explanation.

22.4 Listed below are the data review responsibilities of the Analyst and Peer Reviewer:

22.4.1 Analyst Review is performed by the analyst who generated the data before

the data are submitted for entry into AlphaLIMS. Analyst completes and

attaches the run data cover sheet to the printout.

22.4.2 Peer Analyst Review is performed by an individual who did not perform

the analysis but is familiar with the analytical method used and the

reporting requirements. This person will review the complete data report

after all data are entered, will ensure that any data entry corrections are

made before data are approved, and will complete the reviewer portion of

the data review check list. If the data do not meet the necessary quality

requirements and need further analysis, they are returned to the analyst or

representative.

22.5 A Third Review is performed for Data Packages (level 3 to level 6 CLP-Like)

and/or by client requirement. This review is by the Metals Team Validator or other

qualified person.

22.6 Specific items that are reviewed at each level include the following:

22.6.1 Analyst Review: Before data is submitted for entry into AlphaLIMS.

22.6.1.1 All analyses in the batch are completed.

22.6.1.2 Any corrections and comments on the data are properly initialed

and dated.

22.6.1.3 Proper standard identification numbers appear on the runlog to

ensure traceability from the data to original source standards.

22.6.1.4 All data are complete and accurate in the AlphaLIMS data

report.

22.6.1.5 Data acceptance limit criteria identified in Section 21.2 are met

or an explanation given.

22.6.2 Peer Analyst Review: Before data are submitted for further review or

update:

22.6.2.1 All data are complete and accurate in the AlphaLIMS Data

Report.

22.6.2.2 Any exceptions or shortcomings have been sufficiently

explained or corrected.

22.6.2.3 Data are reported in the proper units or an explanation is given.

22.6.2.4 Prep factor and dilution calculations by AlphaLIMS are present

in the data report and AlphaLIMS calculations are correct.

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22.6.2.5 LCS and Spike Recoveries and RPD calculations by

AlphaLIMS are correct, and the values are within control limits.

22.7 When the data review is completed and the data have been reported out of the lab,

they are bound with the batching sheet and kept on file in the lab.

22.8 The complete data review process requires the use of the Prep Log Book, Prep data

report, batch sheet, AlphaLIMS data report, raw instrument data, and runlog.

23.0 DATA REPORTING

23.1 To report data after the review process has been completed:

23.1.1 Enter the AlphaLIMS program through an available terminal and select

DATA MENU, BATCH ITEMS, CHANGE BATCH STATUS.

23.1.2 Enter the Batch Number and “Submit.”

23.1.3 Use the down arrow key to move the cursor down the new status column to

the end. Change status from REVW to DONE and “Save.”

24.0 RECORDS MANAGEMENT AND DOCUMENT CONTROL

24.1 Records of the instrumental analysis, operation, and maintenance are maintained as

follows:

24.1.1 Run logs are an accurate chronology of what the instrument did during a

specified period of time. The logs detail the standard name or sample

number for each standardization or analysis, the analyst identification, and

the date and time of each analysis or standardization. This information is

periodically retrieved from the instrument data files, printed in

chronological sequence, and maintained as documentation of the sequence

of events and as a reference for the raw data.

24.1.2 Extraction/Digestion Logs are maintained in accordance with the

established procedures in the areas where these processes are performed.

24.1.3 Instrument Maintenance Logs are chronological representations of all

maintenance activities involving the instrument operation. This record is

kept in bound composition books and consists of the details of the action,

who performed it, when it was performed, and when instrument was

returned to operation.

24.1.4 Batch Sheets accompany the batch of samples through digestion and

analysis and then accompany the raw analytical data through data entry and

data review until the batch status is changed to “DONE” in the laboratory.

This record is maintained in the Metals group files.

24.1.5 Batch Data Reports are generated to be used in the peer data review. After

the batch is reviewed, corrected if necessary, and updated to “DONE,” the

batch data report is stored with the Batch sheet.

24.1.6 Raw Instrument Data are generated as the analyses are performed and from

AlphaLIMS after the data are entered and attached to the batch sheet to be

used in the data review process and kept in the Metals group files.

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25.0 LABORATORY WASTE HANDLING AND DISPOSAL: SAMPLES, EXTRACTS,

DIGESTATES, AND REAGENTS

25.1 Standard solutions that must be disposed are taken to the Waste Disposal

coordinator for disposal in accordance with Laboratory Waste Management Plan,

GL-LB-G-001.

25.2 Sample digestates are stored in the lab for a specified period of time following

analysis. At this time, they are composited into a waste container that is picked up

by the Waste Management Technician for proper disposal.

25.3 Radioactive Waste:

25.3.1 Samples returned to sample storage

25.3.2 Drain waste collected in the radioactive waste carboy is dumped when full

into the appropriate 55 gallon drum sitting outside the ICPMS laboratory.

Ultimate disposal of liquid radioactive waste done by waste management

department.

25.3.3 Implements, vials, gloves, etc., are wrapped and labeled with radioactive

tape and placed in the radioactive waste container in high bay area.

25.3.4 Expired Standard Solutions: Refer to Section 25.1.

26.0 REFERENCES

26.1 Perkin Elmer ELAN 9000 Hardware Guide

26.2 Perkin Elmer ELAN 6100 Hardware Guide

26.3 Perkin Elmer ELAN 9000 Software Guide

26.4 Perkin Elmer ELAN 6000/6100 Software Guide

26.5 Test Methods for Evaluating Solid Waste: Laboratory Manual Physical/Chemical

Methods. Volume 1A, USEPA SW-846, Third Edition, Revision 2, September

1994.

26.5.1 Method 6020A, “Inductively Coupled Plasma – Mass Spectrometry,”

Revision 1, February 2007.

26.5.2 Method 6020, “Inductively Coupled Plasma – Mass Spectrometry,”

Revision 0, September 1994.

26.5.3 Method 3005A, “Acid Digestion of Waters for Total Recoverable or

Dissolved Metals for Analysis by FLAA or ICP Spectroscopy”, Revision 1,

July 1992.

26.5.4 Method 3010A, “Acid Digestion of Aqueous Samples and Extracts for

Total Metals for Analysis by FLAA or ICP Spectroscopy,” Revision 1, July

1992.

26.5.5 Method 3050B, “Acid Digestion of Sediments, Sludges, and Soils”,

Revision 2, December 1996.

26.6 USEPA Method 200.8, “Determination of Trace Elements in Waters and Wastes by

Inductively Coupled Plasma – Mass Spectrometry,” Revision 5.4, May 1994.

26.7 2001 Annual Book of ASTM Standard, D4698-92 “Standard Practice for Total

Digestion of Sediment Sampler for Chemical Analysis of Various Metals.”

30-Sep-2013







26.8 Conversion Constants for Uranium Isotopes, Dr. Robert Litman, April 2009.

26.9 Department of Defense Quality Systems Manual for Environmental Laboratories,

Version 4.2, October 25, 2010.

26.10 U.S. Department of Energy, Quality Systems for Analytical Services (DOE QSAS).

Rev 2.6, November 2010.

27.0 HISTORY

Revision 25: Clarifications on analyte lists, internal standards, and method requirements.

Revision 24: Updated section on sample preparation techniques to include procedure GL-

MA-E-016

Revision 23: Updated sections 15.2, 21.2.5 and Appendix 3 to four internal standards.

Removed outdated SOP references.

Revision 22: Editorial corrections only.

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APPENDIX 1: FREQUENCY OF QUALITY CONTROL ACTIVITIES

(For illustrative purposes only)

Frequency of Quality Control Activities

Method/

Frequency

SW-846 6020 EPA 200.8 SW-846 6020A

Calibration Std

readbacks

Not required Not required Not required

ICV Per calibration Per calibration Per calibration

ICB Per calibration Per calibration Per calibration

PQL Per calibration Per calibration Per calibration and at

end of each analytical

batch.

ICSA Per calibration Per calibration Per calibration

ICSAB Per calibration; every 12

hours after

Per calibration Per calibration; every

12 hours after

Linear Range

Standard (LRS)

Per calibration, if

applicable

Per calibration, if

applicable

Per calibration, if

applicable

CCV Every 10 instrument

runs

Every 10

instrument runs

Every 10 instrument

runs

CCB Every 10 instrument

runs

Every 10

instrument runs

Every 10 instrument

runs

Method Blank 5% or per batch 5% or per batch 5% or per batch

LCS – liquid

LCS – soil

5% or per batch 5% or per batch 5% or per batch

Matrix Spikes 5% or per request 10% or per request 5% or per request

Sample Duplicates 5% or per request 5% or per request 5% or per request

Serial Dilutions 5% or per request 5% or per request 5% or per request

Matrix Spike

Duplicates

5% or per request 10% or per request 5% or per request

Post-Digestion

Spikes

5% or per request 10% or per request 5% or per request

30-Sep-2013







APPENDIX 2: ACCEPTANCE LIMITS

Method/

Acceptance

Criteria

SW-846 6020 EPA 200.8 DoD QSM SW-846 6020A

Calibration Std readbacks

Not required Not required Not required Not required

ICV 90% - 110% 90% - 110% 90%-110% 90% - 110%

ICB < absolute value of RL

< absolute value of RL < LOD < absolute value of RL

PQL/CRI (CLP) 70% - 130% advisory limits only

70% - 130% advisory limits only

80%-120% or investigate and recalibrate

70% - 130% or investigate and recalibrate

ICSA 80-120% for major components; ± 2x RL for non-spiked

80-120% for major components; ± 2x RL for non-spiked

80%-120% for major compounds; ± LOD for non-spiked

80-120% for major components; ± 2x RL for non-spiked

ICSAB 80%-120% 80%-120% (may be requested)

80%-120% 80%-120%

Linear Range Standard (LRS)

90%-110%, or up to the high calibration standard




CCV 90% - 110% 90% - 110% 90%-110% 90% - 110%

CCB ± RDL ± RDL < LOD ± RDL

Method Blank ± RDL ± RDL ± ½ RL except for Al, Fe, Mg, Ca, Na, and K

± RDL

LCS - liquid LCS - soil

80% - 120% current SPC limits

85% - 115% current SPC limits

80%-120% 80% - 120% current SPC limits

Matrix Spikes 75% - 125%, when applicable

75% - 125%, when applicable

80%-120% 75% - 125%, when applicable

Sample Duplicates 0% - 20% when greater than 5X RL,

± RL when less than 5X RL

0% - 20% when

greater than 5X RL, ±RL when less than 5X RL

0% - 20% when


0% - 20% when greater than 5X RL,


Serial Dilutions 0% - 10% of initial raw value, when applicable

0% - 10% of initial raw value, when applicable

0% - 10% of initial raw value, when applicable (> 50x LOQ)

0% - 10% of initial raw value, when applicable

Post-digestion spikes

75%-125%, when applicable

75%-125%, when applicable

75%-125% 80%-120%, when applicable

Internal Standards 30%-120%, samples 80%-120% for ICB, ICV, CCV, CCB

60%-125% for all 30%-120% 70%-130%, for all

Matrix Spike Duplicate



0% - 20% when


0% - 20% when




30-Sep-2013







APPENDIX 2-Cont’d

Method/

Acceptance

Criteria

SW-846 6020 EPA 200.8 DoD QSM SW-846 6020A

Sample Duplicates RER activity

≤ 3% ≤ 3% ≤ 3% ≤ 3%

30-Sep-2013







APPENDIX 3: INTERNAL STANDARDS WITH ASSOCIATED ANALYTES/ISOTOPES

*(calc) – isotope used in calculations

IS 45

Sc IS 74

Ge IS 115

In IS 175

Lu 181

Ta 7Li

66Zn

88Sr

133Cs

9Be

67Zn (calc)

90Zr

135Ba (calc)

11B

68Zn (calc)

98Mo

137Ba

23Na

75As

105Pd

139La

24Mg

77Se (calc)

107Ag

140Ce

27Al

82Se

111Cd

141Pr

31P

83Kr (calc)

114Cd (calc)

142Nd

39K

120Sn

152Sm

43Ca

121Sb

153Eu

47Ti

123Sb (calc)

158Gd

52Cr

159Tb

53Cr (calc)

178Hf

55Mn

187Re

57Fe

195Pt

59Co

197Au

60Ni

205Tl

63Cu (calc)

208Pb

65Cu

209Bi

232

Th

233

U

234

U

235

U

236

U

238

U

30-Sep-2013







APPENDIX 4: RADIOCHEMISTRY CONVERSION CALCULATIONS FOR

URANIUM ISOTOPES

Conversion for liquids (µg/L x CF = pCi/L)233

U (µg/L to pCi/L) = 9640.6 234

U (µg/L to pCi/L) = 6224.9 235

U (µg/L to pCi/L) = 2.1615 236

U (µg/L to pCi/L) = 64.698 238

U (µg/L to pCi/L) = 0.33627

Conversion for solids (mg/kg x CF = pCi/g)233

U (mg/kg to pCi/g) = 9640.6 234

U (mg/kg to pCi/g) = 6224.9 235

U (mg/kg to pCi/g) = 2.1615 236

U (mg/kg to pCi/g) = 64.698 238

U (mg/kg to pCi/g) = 0.33627

30-Sep-2013

Acid Digestion of Sediments, Sludges, and Soils SOP Effective 8/93 GL-MA-E-009 Rev 22

Revision 22 Effective May 2013 Page 1 of 13







FOR

ACID DIGESTION OF

SEDIMENTS, SLUDGES, AND SOILS

(GL-MA-E-009 REVISION 22)

APPLICABLE TO METHODS: EPA SW-846 3050B Modified


This document contains proprietary information that is the exclusive property of GEL Laboratories, LLC (GEL). No contents of this document may be reproduced or otherwise used for the benefit of others except by express written permission of GEL.

30-Sep-2013







TABLE OF CONTENTS

1.0 STANDARD OPERATING PROCEDURE FOR ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS ................................................................................................................... 3

2.0 METHOD CODE............................................................................................................................... 3

3.0 MEHTOD OBJECTIVE/PURPOSE.................................................................................................. 3

4.0 METHOD SUMMARY..................................................................................................................... 3

5.0 APPLICABLE MATRICES .............................................................................................................. 3

6.0 HOLD TIME...................................................................................................................................... 4

7.0 SAMPLE CONTAINER/PRESERVATION/COLLECTION/STORAGE REQUIREMENTS........ 4

8.0 INTERFERENCES............................................................................................................................ 4

9.0 PERFORMANCE CHARACTERISTICS......................................................................................... 4

10.0 DEFINITIONS................................................................................................................................... 4

11.0 ANALYST VERIFICATION ............................................................................................................ 5

12.0 DOCUMENTATION OF DATA ...................................................................................................... 5

13.0 SAFETY, HEALTH, AND ENVIRONMENTAL HAZARDS......................................................... 5

14.0 SAMPLE RECEIPT FOR ANALYSIS ............................................................................................. 6

15.0 INSTRUMENT/EQUIPMENT/GLASSWARE ................................................................................ 6

16.0 REAGENTS....................................................................................................................................... 7

17.0 PREPARATION OF SAMPLES ....................................................................................................... 7

18.0 PREPARATION OF STANDARDS ................................................................................................. 9

19.0 INSTRUMENT/EQUIPMENT START-UP PROCEDURE ........................................................... 10

20.0 QUALITY CONTROL (QC) REQUIREMENTS ........................................................................... 10

21.0 RUN SEQUENCE ........................................................................................................................... 10

22.0 PROCEDURE.................................................................................................................................. 10

23.0 INSTRUMENT/EQUIPMENT SHUT-DOWN PROCEDURE...................................................... 10

24.0 METHOD VARIATION ................................................................................................................. 11

25.0 DATA REVIEW, VALIDATION, AND APPROVAL PROCEDURE.......................................... 11

26.0 RECORDS MANAGEMENT ......................................................................................................... 11

27.0 LABORATORY WASTE................................................................................................................ 11

28.0 REFERENCES................................................................................................................................. 11

29.0 HISTORY ........................................................................................................................................ 12

APPENDIX 1: SAMPLE PREP LOGBOOK............................................................................................ 13

30-Sep-2013







1.0 STANDARD OPERATING PROCEDURE FOR ACID DIGESTION OF SEDIMENTS,

SLUDGES, AND SOILS

2.0 METHOD CODE

2.1 EPA SW-846 3050B Modified

3.0 METHOD OBJECTIVE/PURPOSE

To describe the manner in which sediments, sludges, and soils for Inductively Coupled

Plasma (ICP) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) analysis are

digested by EPA SW-846 Method 3050B Modified. Samples digested by this procedure

are applicable for analysis by SW-846 methods 6010B and 6020. Included in this

standard operating procedure is guidance for paint and jewelry preparation.

4.0 METHOD SUMMARY

A representative portion of sample is digested with nitric acid and hydrogen peroxide.

This digestate is then refluxed with hydrochloric acid for ICP analysis only. Samples

prepared by this method may be analyzed for all the listed metals. Other metals may be

analyzed if they pass control standard criteria:

Aluminum Copper Palladium Terbium

Antimony Europium Phosphorus Tin

Arsenic Gold Platinum Thorium

Barium Hafnium Praseodymium Titanium

Beryllium Iron Rhenium Thallium

Bismuth Lanthanum Ruthenium Tungsten

Boron Lead Samarium Uranium

Boron-10 Lithium Selenium Uranium-233

Cadmium Magnesium Silica Uranium-234

Calcium Manganese Silicon Uranium-235

Cerium Molybdenum Sulfur Uranium-236

Cesium Neodynium Sodium Uranium-238

Chromium Potassium Silver Vanadium

Cobalt Nickel Strontium Zinc

Zirconium

This method is not a “total” digestion technique for most samples. It is a very strong acid

digestion that will dissolve all elements that could become “environmentally available”

by design; elements bound in silicate structures (boron, silicon, silica) are not normally

dissolved by this procedure as they are not usually mobile in the environment.

5.0 APPLICABLE MATRICES

5.1 Soils

5.2 Sludges

30-Sep-2013







5.3 Sediments

5.4 Solid debris/powders

5.5 Heavy oils

5.6 Filters

5.7 Paints

5.8 Metal jewelry

6.0 HOLD TIME

Holding time is 180 days from the time and date of collection until the start of analysis

unless otherwise specified by contract.

7.0 SAMPLE CONTAINER/PRESERVATION/COLLECTION/STORAGE

REQUIREMENTS

Solid samples are not preserved but should be stored at 0°- 6° C.

8.0 INTERFERENCES

There are rarely any interferences with this digestion. If any are encountered, consult the

group leader or quality officer before continuing.

9.0 PERFORMANCE CHARACTERISTICS

Method detection limits (MDLs) are performed annually and method detection limit

verification (MDLVs) are performed quarterly.

10.0 DEFINITIONS

10.1 Blank: Type I water that has been taken through the digestion process. The blank

is used to determine the amount of background contamination.

10.2 Laboratory Control Sample (LCS): A certified reference material that has been

taken through the digestion process. The LCS is used to determine digestion

accuracy and to determine if the digestion process is in control.

10.3 Laboratory Control Sample Duplicate (LCS DUP): A duplicate of the LCS. The

LCS DUP is used to determine reproducibility and to indicate precision.

10.4 Matrix Spike (MS): A sample that has added to it a known amount of solution

containing known concentrations of analytes. The MS is used to determine the

presence or absence of interferences and matrix effects in the digested sample.

10.5 Matrix Spike Duplicate (MSD): A duplicate of the MS. The MSD indicates

reproducibility.

10.6 Sample Duplicate (DUP): A duplicate of a sample. The DUP indicates

reproducibility.

10.7 AlphaLIMS: The Laboratory Information Management System used at GEL.




30-Sep-2013







11.0 ANALYST VERIFICATION

Before a technician/analyst is allowed to analyze samples without supervision, he or she

is trained by qualified personnel and is required to successfully analyze a proficiency

sample. Training records are maintained as quality records (Refer to GL-QS-E-008).

12.0 DOCUMENTATION OF DATA

Sample preparation data are recorded in AlphaLIMS.

13.0 SAFETY, HEALTH, AND ENVIRONMENTAL HAZARDS

WARNING

CONCENTRATED HYDROCHLORIC ACID AND NITRIC ACID ARE EXTREMELY CORROSIVE AND CAN CAUSE SEVERE BURNS TO THE SKIN.

CONCENTRATED 30% HYDROGEN PEROXIDE IS A VIOLENT OXIDIZER. KEEP AWAY FROM OPEN FLAMES, AND RINSE WITH WATER IF SKIN CONTACT OCCURS.

13.1 Wear eye protection with side shields while performing procedures in the lab.

13.2 Treat all chemicals and samples as potential health hazards, and reduce exposure

to these chemicals to the lowest level possible. GEL maintains a current

awareness file of OSHA regulations regarding the safe handling of the chemicals.

A reference file of Material Safety Data Sheets (MSDS) and individual client

sample MSDSs are also maintained.

13.3 Personal protective equipment

13.3.1 Disposable gloves are worn and changed frequently when working with

acids, glassware, or samples. Dirty gloves pose a contamination hazard

to the samples. Gloves that have holes can be dangerous to the wearer by

allowing acids and toxic metals to come in contact with skin.

13.3.2 Hood doors are pulled down partially while digesting samples. Acidified

samples can splash and pop as they are being heated.

13.3.3 To protect clothes and skin from exposure to corrosive material, wear a

lab jacket.

13.4 Prior to handling radioactive samples, analysts must have had radiation safety

training and must understand their full responsibilities in radioactive sample

handling. Some general guidelines follow:

13.4.1 Wear plastic apron over lab coat when working with radioactive samples.

13.4.2 Protect counter tops with counter paper, or work from radioactive sample

handling trays.

13.4.3 Prohibit admittance to immediate work area.

13.4.4 Post signs indicating radioactive samples are in the area.

13.4.5 Take swipes of the counter tops upon completion of work. Deliver those

swipes to the designated swipe count box.

13.4.6 Segregate radioactive wastes. Radioactive waste containers are obtained

from the Waste Management.

30-Sep-2013







13.5 All samples, chemicals, extracts, and extraction residues must be transferred,

delivered, and disposed of safely according to all related SOPs.

13.5.1 Segregate solid wastes from liquid wastes in the satellite area containers.

13.5.2 Segregate oil wastes from water-soluble wastes in the satellite area

containers.

13.6 In the event of an accident or medical emergency, call for help immediately.

When time and safety permit, an accident report form should be completed and

turned in to the safety committee.

13.7 Fire escape routes are posted in the lab, and all personnel should be familiar with

them. In addition, fire safety equipment such as fire extinguishers is located in the

lab. Training is available on the proper operation of this equipment.

14.0 SAMPLE RECEIPT FOR ANALYSIS

14.1 The analyst/technician submits the list of samples needed to the sample custodian

group. The sample custodian removes the appropriate sample from the cooler and

scans it using the barcode scanner to the appropriate area of the lab. The analyst

then takes custody of the samples and scans them to the sample batch. The

samples are now ready to be prepared or analyzed.

14.2 Analysts/technicians are responsible for retrieving their own samples when the

sample custodian is unavailable.

15.0 INSTRUMENT/EQUIPMENT/GLASSWARE

15.1 Equipment

15.1.1 Air displacement pipettes

15.1.1.1 5-10 mL with disposable tips

15.1.1.2 0.5-5 mL with disposable tips

15.1.1.3 100-1000 µL with disposable tips

15.1.1.4 10-100 µL with disposable tips

15.1.2 Environmental Express hot blocks or equivalent

15.1.3 Analytical balance capable of reading to three decimal places

15.1.4 Certified disposable 50 mL digestion tubes (polypropylene)

15.1.5 Ribbed disposable watch glasses (polypropylene)

15.1.6 Water resistant lab markers

15.1.7 Styrofoam trays to handle up to 25 digestion tubes

15.1.8 500 mL Nalgene squirt bottle

15.1.9 Teflon chips

15.1.10 1-inch white laboratory tape

15.1.11 Borosilicate beakers (various sizes)

15.1.12 Borosilicate watch glasses (various sizes)

30-Sep-2013







16.0 REAGENTS

16.1 Nitric acid (HNO3), concentrated high purity grade 70% nitric acid

16.2 Hydrochloric acid (HCl), concentrated high purity grade 37% hydrochloric acid

16.3 Hydrogen peroxide (H2O2), concentrated 30% hydrogen peroxide

16.4 Type I deionized (DI) water.

16.5 Multi-element spiking solutions are purchased from NIST-traceable vendors.

17.0 PREPARATION OF SAMPLES

A batch consists of samples of the same matrix and quality control (QC) samples that are

digested together. Each of the quality control samples listed in steps 10.1 through 10.6

must be included in each batch at the frequency listed or as per client request. The blank,

LCS, and/or LCS DUP are digested at a frequency of one in 20 or per batch, whichever is

more frequent. The MS, MSD, and/or DUP are digested at a frequency of one in 20 or

per batch, whichever is more frequent, or per specified client/program requirements.

17.1 Glassware preparation:

17.1.1 Glassware that has been cleaned according to GL-LB-E-003 for Glassware

Preparation is soaked in a water and acid mixture for at least 30 minutes.

17.1.2 After soaking, the glassware is rinsed with copious quantities of Type I

water and then inverted over clean, absorbent paper or onto a rack for

drying.

17.2 Label the Teflon beakers or centrifuge tube with the sample numbers in the batch.

If centrifuge tube is to be used for measuring initial and final volumes it must be

calibrated before usage. Refer to GL-LB-E-026 for centrifuge tube testing

procedure.

17.3 Refer to GL-LB-E-029 for subsampling instructions. Mix the sample to achieve

homogeneity. Weigh approximately 0.5 g of sample. Transfer the weighed

sample to the appropriately labeled Teflon beaker or centrifuge tube.

17.3.1 Sample aliquots should not be taken from the top of an unmixed sample

because large particles tend to rise in solid matrixes and heavy materials

tend to sink in liquid matrixes.

17.3.2 Powdered samples may be homogenized by gently rocking the sample side

to side. Then a representative aliquot may be taken from the center of the

powder.

17.3.3 Other matrixes must be stirred, turned or mixed before sampling.

17.4 Quality control samples are prepared prior to digestion.

17.4.1 The beaker or tube to be used for the blank, MS, MSD, and/or DUP, LCS,

and/or LCS DUP is labeled.

17.4.2 Weigh approximately 0.5 g of sample and transfer to the MS, MSD, and/or

DUP beaker or tube.

The MS, MSD, LCS, and/or LCS DUP are spiked with known amounts of

spiking solution.

30-Sep-2013







17.4.3 Select a LCS. The LCS is purchased for an outside vendor and comes with

a certificate of certified values and recovery ranges. The LCS is logged

into the AlphaLIMS system for traceability and for the use of nominal

calculations. For analytes not certified in the Solid Reference Material

(SRM), a series of 20 preparations and analyses are conducted and an

average concentration is determined. A value of 3 times the standard

deviation is used as control limits for the LCS recovery for these analytes.

Mix the LCS to achieve homogeneity. Weigh approximately 0.5 g of the

sample and transfer to the LCS and/or LCS DUP Teflon beaker or

centrifuge tube. For non-soil solid samples, a liquid LCS is used in

combination with approximately 0.5 g of Teflon chips.

17.4.4 The blank beaker or tube is labeled and no water, spike, or sample is added

to it. Approximately 0.5 g of Teflon chips is used.

17.5 If the samples are being prepared for ICP-MS analysis:

17.5.1 Add 2.5 mL nitric acid and Type I DI water to the samples and quality

control samples.

17.5.2 Gently swirl the sample and acid mixture.

17.5.3 Cover the sample with a watch glass and heat the sample on a hot

plate/block to 95° ± 5° C. Reflux the sample for 10 to 15 minutes.

17.5.4 Remove the sample from the hot plate or block and allow the sample to

cool.

17.5.5 Add 2.5 mL of concentrated nitric acid, replace the watch glass, and

reflux for 30 minutes. If brown fumes are generated indicating oxidation

of the sample by nitric acid, repeat step 17.5.5 over and over until no

brown fumes are given off by the sample.

17.5.6 Using a ribbed watch glass or vapor recovery system, allow the solution

to evaporate to approximately 0.5 mL without boiling, or heat for 2

hours.

17.5.6.1 Remove the sample from the hot plate or block and allow the

sample to cool.

17.5.6.2 Add 1.5 mL of hydrogen peroxide and 1.0 mL of Type I water.

Return the sample to the hot plate or block and allow the

peroxide reaction to occur. Continue to add hydrogen peroxide

to the sample until the effervescence subsides. Do not add

more than 5 mL hydrogen peroxide.

17.5.6.3 Cover the sample with a ribbed watchglass, heating the acid-

peroxide digestate until the volume is reduced to approximately

2.5 mL, or heat at 95° ± 5° C without boiling for 2 hours.

17.5.6.4 Do not allow the sample to evaporate to dryness.

17.5.6.5 Remove the sample from step 17.5.6.3 from the hot plate or

block.

30-Sep-2013







17.5.6.6 Allow the sample to cool.

17.5.6.7 Dilute the sample to 50 mL with Type I water.

17.5.6.8 Cap and shake the sample.

17.5.6.9 Filter each sample with a 2.0 µm pore size plunger type filter

(PTF grade) or allow to settle overnight.

17.5.6.10 Organize the samples in a storage container, and label the

container with the batch number of the sample group.

17.6 If the samples are being prepared ICP analysis:

17.6.1 Add 1.25 mL nitric acid and 10 mL hydrochloric acid to the samples and

quality control samples.

17.6.2 Gently swirl to mix.

17.6.3 Cover the sample with a watch glass and heat the sample on a

hotplate/block to 95° ± 5° C. Reflux the sample for 30 minutes.

17.6.4 Remove the sample from the hotplate/block and allow to cool.

17.6.5 Dilute the sample to 50 mL with Type I water.

17.6.6 Cap and shake the sample.

17.6.7 Filter each sample with 2.0 µm pore size plunger type filter (PTF grade)

or allow to sit overnight.

17.6.8 Organize the samples in a storage container, and label the container with

the batch number of the sample group.

17.7 If the sample contains particulate material that could clog the nebulizer, you may

filter or centrifuge the sample if necessary.

17.8 Be advised that filtration is a common cause of contamination. If a sample is

filtered, any QC associated with the sample must also be filtered. Additionally, if

any sample in the batch is filtered the method blank and laboratory control sample

must also be filtered.

17.9 Filters may be prepared via this method. If the filters are small enough to fit

inside the 50 mL digestion tubes, they can be treated as any solid prep materials.

If the filters are too big to undergo adequate digestion using the 50 mL digestion

tube, a borosilicate beaker will need to be used. All reagents and standards will

need to be adjusted for any extra volumes needed. All filter analyses should be

discussed and the process verified with the group/team leader prior to digestion.

The group leader or project manager may have to contact the client to get the full

description of what is required.

18.0 PREPARATION OF STANDARDS

Documentation of standards and their preparation is maintained in AlphaLIMS in

accordance with GL-LB-E-007 for Laboratory Standards Documentation.

30-Sep-2013







19.0 INSTRUMENT/EQUIPMENT START-UP PROCEDURE

Hot plates/blocks are allowed to come to the proper temperature before digestions are

started. The temperatures are monitored before and after a daily digestion session.

20.0 QUALITY CONTROL (QC) REQUIREMENTS

20.1 Frequency of QC

20.1.1 A matrix spike (MS) and a matrix spike duplicate (MSD) or a sample

duplicate (DUP) and a matrix spike are prepped for every batch of < 20

samples

20.1.2 A method blank (MB) and a laboratory control standard (LCS) are

prepped for every batch of < 20 samples. A laboratory control standard

duplicate (LCSD) is prepared if matrix QC is unavailable or upon client

request.

20.2 Makeup of QC Samples

20.2.1 Sample duplicate (DUP) is a separate aliquot taken through the prep

process exactly the same as the original sample.

20.2.2 Matrix spike and/or matrix spike duplicate is a separate aliquot of the

sample to which appropriate spike volumes and solutions are added. The

ID numbers and volumes of the spikes are recorded in the prep logbook.

20.2.3 The method blank (MB) is a reagent blank taken through the same prep

process as the samples. Teflon chips are used to approximate matrix

weights of 0.5 g.

20.2.4 The laboratory control standard (LCS) is a standard performed two

different ways. For DOE-ALB clients, a purchased SRM is used at

approximately 0.5 g and is taken through the same process as the

samples. For all other clients, Teflon chips weighted to approximately

0.5 g are used. The chips and acid solution is spiked with the appropriate

spike volumes and solutions. The ID number and volumes of the spikes

are recorded in the prep logbook.

20.3 Handling Out-Of-Control Situations

If sample reactions cause popping or splattering of the digestate, discontinue the

prep and contact team leader or group leader.

21.0 RUN SEQUENCE

Not applicable

22.0 PROCEDURE

Refer to section 17.0, Preparation of Samples

23.0 INSTRUMENT/EQUIPMENT SHUT-DOWN PROCEDURE

Before turning off the hotplate/blocks at the end of the day, a final monitoring

temperature is recorded for each plate/block that was utilized.

30-Sep-2013







24.0 METHOD VARIATION

24.1 This procedure deviates from method 3050B in that sample volumes are half the

method recommendations.

24.2 The ICP procedure references a modified 3050B section 7.5 procedure. The

modification eliminates the use of the Whatman 41 filters, thus eliminating

contamination of common minerals.

25.0 DATA REVIEW, VALIDATION, AND APPROVAL PROCEDURE

25.1 Upon completion of batch preparation, digestion data shall be entered into the

AlphaLIMS Prep Logbook (refer to Appendix 1) following the guidelines in GL-

LB-E-008 for Basic Requirements for the Use and Maintenance of Laboratory

Notebooks, Logbooks, Forms, and Other Recordkeeping Devices.

25.2 Data to be entered into the electronic logbook include analyst name, prep data and

time, initial volume or weight with units, and final volume with units.

25.3 Standards and reagents may also be entered into the logbook and fall under the

guidelines of GL-LB-E-015 for Control of Laboratory Standards and GL-LB-E-

007 for Laboratory Standards Documentation.

25.4 Upon entry of prep data, obtain a printout of the logbook. The analyst listed on

the logbook should sign and date the page near their printed initials. The logbook

page is kept with the samples with which it is associated.

25.5 The entry of correct prep data is peer reviewed (correct dates, times, weights,

volumes, SOP/revision, spikes, spike amounts, and reagent information, etc.)

Once data are reviewed, the batch is statused to DONE in AlphaLIMS, the

logbook is signed and dated by the reviewer, and the batch is ready for analysis.

A copy of the prep logbook sheet is kept in the metals prep lab and is bound and

given a control number when sufficient numbers of sheets are collected.


Records generated as a result of this procedure are maintained as quality documents in

accordance with GL-QS-E-008 for Quality Records Management and Disposition.

27.0 LABORATORY WASTE

For the proper disposal of sample and reagent wastes from this procedure, refer to the

Laboratory Waste Management Plan, GL-LB-G-001.

28.0 REFERENCES

28.1 Test Method for Evaluating Solid Waste; Laboratory Manual Physical/ Chemical

Methods, Method 3050B, “Acid Digestion of Sediments, Sludges, and Soils,”

Revision 2, December 1996.

28.2 1992 Annual Book of ASTM Standards, Standard D1193-91, “Standard

Specification for Reagent Water.”

28.3 16 CFR Part 1303

30-Sep-2013







29.0 HISTORY

Revision 21: Updated performance characteristics section; MDLs are performed annually

and MDLVs are performed quarterly.

Revision 22: Removed 16 CFR Part 1303 reference.

Revision 22: Clarified DI water. Updated metals list of elements in method summary

section.

30-Sep-2013







APPENDIX 1: SAMPLE PREP LOGBOOK

(For illustrative purposes only)

30-Sep-2013

Gamma Spectroscopy System Operation

SOP Effective December 1999 GL-RAD-I-001 Rev 19

Revision 19 Effective January 2013 Page 1 of 11




Uncontrolled documents do not bear an original set ID number.



FOR

GAMMA SPECTROSCOPY SYSTEM OPERATION

(GL-RAD-I-001 REVISION 19)



Laboratories LLC. No contents of this document may be reproduced or otherwise used

for the benefit of others except by express written permission of GEL.

30-Sep-2013








TABLE OF CONTENTS

1.0 STANDARD OPERATING PROCEDURE FOR GAMMA SPECTROSCOPY SYSTEM

OPERATION..................................................................................................................................... 3

2.0 METHOD OBJECTIVE, PURPOSE, CODE AND SUMMARY..................................................... 3

3.0 APPLICABLE MATRIX OR MATRICES ....................................................................................... 3

4.0 METHOD SCOPE, APPLICABILITY AND DETECTION LIMIT ................................................ 3

5.0 METHOD VARIATIONS ................................................................................................................. 3

6.0 DEFINITIONS................................................................................................................................... 3

7.0 INTERFERENCES/LIMITATIONS ................................................................................................. 3

8.0 SAFETY PRECAUTIONS AND WARNINGS................................................................................ 3

9.0 APPARATUS, EQUIPMENT AND INSTRUMENTATION........................................................... 4

10.0 REAGENTS AND STANDARDS .................................................................................................... 4

11.0 SAMPLE HANDLING AND PRESERVATION ............................................................................. 4

12.0 SAMPLE PREPARATION ............................................................................................................... 4

13.0 QUALITY CONTROL SAMPLES AND REQUIREMENTS.......................................................... 4

14.0 INSTRUMENT CALIBRATION, STANDARDIZATION AND PERFORMANCE...................... 4

15.0 PROCEDURE FOR ANALYSIS AND INSTRUMENT OPERATION........................................... 9

16.0 EQUIPMENT AND INSTRUMENT MAINTENANCE .................................................................. 9

17.0 DATA RECORDING, CALCULATION AND REDUCTION METHODS .................................. 10

18.0 POLLUTION/CONTAMINATION ................................................................................................ 10

19.0 DATA REVIEW, APPROVAL AND TRANSMITTAL ................................................................ 10

20.0 CORRECTIVE ACTION FOR OUT-OF-CONTROL OR UNACCEPTABLE DATA................. 10

21.0 CONTINGENCIES FOR HANDLING THESE SITUATIONS ..................................................... 10

22.0 RECORDS MANAGEMENT ......................................................................................................... 10

23.0 LABORATORY WASTE HANDLING AND DISPOSAL............................................................ 10

24.0 REFERENCES................................................................................................................................. 10

25.0 HISTORY ........................................................................................................................................ 11

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1.0 STANDARD OPERATING PROCEDURE FOR GAMMA SPECTROSCOPY SYSTEM

OPERATION

2.0 METHOD OBJECTIVE, PURPOSE, CODE AND SUMMARY

2.1 This standard operating procedure provides the necessary instructions to conduct

the analysis for gamma isotopes using the Gamma Spectroscopy System.

2.2 Gamma emitting isotopes within the sample matrix are identified and quantified

using gamma spectrometry. A sample aliquot is placed in a calibrated geometry

and placed in the detector chamber. The germanium crystal therein produces a

corresponding electrical pulse for the gamma photons that interact with the

detector. The cumulative pulses are analyzed using software capable of

quantifying gamma-emitting isotopes from the spectral data.

3.0 APPLICABLE MATRIX OR MATRICES

This is a nondestructive test for the measurement of gamma emitting isotopes in all

matrices for which there is an available calibration standard.

4.0 METHOD SCOPE, APPLICABILITY AND DETECTION LIMIT

4.1 The aliquoted sample activity or sample position should be adjusted so that the

detector system dead time remains less than 15%.

4.2 Method Detectable Activity: The MDA is based upon sample volume, instrument

background, detector efficiency, count time and other statistical factors, as well as

specific isotopic values such as abundance and half-life.

5.0 METHOD VARIATIONS

Not applicable

6.0 DEFINITIONS

6.1 Abundance: The combination of the isotopic decay branching ratio and the

expected gamma emissions per disintegration of an isotope at a particular energy.

6.2 Key Line: The line chosen by the builder of the library to be the prominent line

of the isotope. This line is used for the purposes of calculating activity, error and

MDA.

6.3 AlphaLIMS: The Laboratory Information Management System used to store and

report data.




7.0 INTERFERENCES/LIMITATIONS

7.1 Some gamma isotopes emit gamma lines that may overlap with those from other

isotopes. If the energies of the two isotopes are within the energy tolerance

setting, the peaks may not be resolvable and may give a positive bias to the result.

This problem is minimized by careful review of the peak search.

8.0 SAFETY PRECAUTIONS AND WARNINGS

Follow safety precautions as outlined in GL-LB-N-001 for the Safety, Health and

Chemical Hygiene Plan.

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9.0 APPARATUS, EQUIPMENT AND INSTRUMENTATION


9.1.1 Compaq/DEC Alpha Station with OpenVMS

9.1.2 Canberra Genie-ESP Application Software

9.1.3 High purity germanium detector

9.1.4 Pulse processing electronics

10.0 REAGENTS AND STANDARDS

10.1 Standards

10.1.1 NIST traceable mixed gamma standards in geometries and densities,

closely approximating analytical samples, used to calibrate the

instrument.

11.0 SAMPLE HANDLING AND PRESERVATION

Refer to GL-RAD-A-013 The Determination of Gamma Isotopes.

12.0 SAMPLE PREPARATION


13.0 QUALITY CONTROL SAMPLES AND REQUIREMENTS


14.0 INSTRUMENT CALIBRATION, STANDARDIZATION AND PERFORMANCE

14.1 Calibration Standard

14.1.1 Mixed Gamma calibrations typically use a standard with 8-12 photons

emitted over a range from approximately 45 keV to approximately 2000

keV.

14.1.2 Single nuclide calibrations typically use a standard comprised of the

nuclide of interest.

14.2 Verification Standard

14.2.1 Mixed Gamma calibrations- A second source (from

different manufacturer or if from the same manufacturer, a

different lot number) is used for verification. The lines from Am-241, Cs-

137 and Co-60 are used to verify the efficiency curve. These encompass

the low, middle and high portions of the energy range.

14.2.2 Single nuclide calibrations – A second source (from a

different manufacturer or if from the same manufacturer, a

different lot number) is used for verification.

14.3 Standardization

14.3.1 High Voltage Adjust

14.3.1.1 See appropriate instrument manual for operation of

electronics.

14.4 Calibration – Energy and efficiency calibrations are performed annually, upon

initial instrument setup, after major repair or service, or when performance checks

indicate a need.

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NOTE: Expiration dates will match the last day of the month in which the

calibration data was acquired.

14.4.1 Count Calibration Spectrum

14.4.1.1 Place the radioactive source on the detector.

14.4.1.2 Select Calibration Count a Calibration Standard from

the Calibration menu and click OK.

14.4.1.3 Enter the Preset Live (secs): in seconds and click OK.

Count the standard until a minimum of 10,000 counts is

acquired in each peak of interest.

14.4.2 Initial Energy & Shape Calibration

14.4.2.1 Select Calibration Initial Energy & Shape Calibration

from the Calibration menu and click OK.

14.4.2.2 Select the detector.

14.4.2.3 Select the Certificate File from the drop down list. Click

OK.

14.4.2.4 From the Energy Calibration dialog box highlight one of

the energy lines listed.

14.4.2.5 Move the cursor in the MCA window to the corresponding

channel expected for that energy line.

14.4.2.5.1 The apex of the peak of interest should be at

the expected channel.

14.4.2.5.2 From the Energy Calibration dialog box

click the Cursor button.

14.4.2.6 Repeat the previous step until all energy lines listed have

been referenced with a corresponding channel.

14.4.2.7 From the Energy Calibration dialog box select the OK

button.

14.4.2.8 The system will ask “Do you want to do a full energy and

shape calibration?” Select YES.

14.4.2.9 The energy and shape calibrations will now be performed

with all of the lines from step 14.4.2.6. Verify the energy

and shape curve generated. Select OK to continue or

Cancel to abort the calibration.

14.4.2.10 A new page will appear with the Energy Calibration

Report and the FWHM Calibration Report. Review the

columns marked difference. For the energy calibration, the

absolute value of the difference must be less than 1.0 and

for the FWHM calibration, the absolute value of the

difference must be less than 0.5. Regardless of the results,

select Dismiss.

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14.4.2.11 A new pop-up screen will appear. If the results from the

previous step were less than a 0.2 keV difference, select

OK. If the results were greater than a 0.2 keV difference

select Cancel and begin the energy calibration process

again at step 14.4.1.

14.4.3 Energy Re-Calibrate

14.4.3.1 Select Calibrate Re-Calibrate Energy and Shape

Calibration from the main menu and click OK.

14.4.3.2 Select the detector.

14.4.3.3 Select the certificate file and select the OK button.

14.4.3.4 The energy and shape calibrations will now be performed

with all of the lines from step 14.4.2.6. Verify the energy

and shape curve generated. Select OK to continue or

Cancel to abort the calibration.

14.4.3.5 A new page will appear with the Energy Calibration

Report and the FWHM Calibration Report. Review the

columns marked difference. For the energy calibration, the

absolute value of the difference must be less than 1.0 and

for the FWHM calibration, the absolute value of the

difference must be less than 0.5. Regardless of the results,

select Dismiss.

14.4.3.6 A new pop-up screen will appear. If the results from the

previous step were less than a 0.2 keV difference, select

OK. If the were greater than a 0.2 keV difference select

Cancel and begin the energy calibration process again. If it

fails after re-calibration contact Group or Team Leader for

further instructions.

14.4.4 Efficiency Calibrate

14.4.4.1 Select Calibrate Efficiency Calibrate from the main

menu.

14.4.4.2 Select the geometry that represents the standardized

radioactive source and click OK. If the geometry doesn’t

exist select Create New Geometry, enter the name of the

new geometry and select OK.

14.4.4.3 Select the certificate for the calibration standard and select

the OK button.

14.4.4.4 The efficiency calibration curve will be displayed for

review. Select Empirical fit, and Log scale.

14.4.4.5 To accept the calibration select OK, or select Cancel to

abort.

14.4.4.6 Dismiss the Calibration report displayed to complete the

calibration procedure.

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14.4.4.7 In the DECterm type EFFPlot, then press ENTER the type

EFFPRINT then hit ENTER. This will print the efficiency

curve.

14.4.5 Efficiency Verifications

14.4.5.1 Verification counts are performed as a normal sample count

starting at step 15.2.3 of this SOP.

14.4.5.2 No batch ID is assigned to verification counts, typically

“VER” is used.

14.4.5.3 Select the only sample identification available regardless of

how it is named.

14.4.5.3.1 You may be asked if you would like to

extend the count. Select NO.

14.4.5.3.2 When the screen to enter the sample

information appears (step 15.2.8), use the

date and time indicated on the

manufacturer’s certificate file for decay

correction and change the sample

identification using the following naming

convention:

VER_DETECTOR_GEOMETRY, for

example VER_GAM01_CAN.

14.4.5.4 Once the count has completed, in the DECterm, type

“@print_virtual sample, where sample equals the same

identification used in step 14.4.5.3.2. This will print out the

raw data of the verification count.

14.4.5.5 Several pages will print out. The only pages needed are the

background-subtracted peak report, which should be the

first page, and the nuclide line activity report.

14.4.5.6 Place the results from the “Decay Corr” column into the

appropriate Master Verification Spreadsheet located at

S:\RAD\FORMS\EFF_VER where S:= sdrive on

‘radserver’ under the column named Measured Activity.

14.4.5.7 If necessary, enter the emission rate for the standard used

for verification on the Master Verification Spreadsheet.

This can be found on the manufacturer’s certificate file for

the standard. The spreadsheet will then calculate the

Calibrated Activity. If a column for the emission rate does

not exist on the spreadsheet, the Calibrated Activity can

be calculated by using the values from the Decay Correct

Source page in Alpha LIMS

(http://prodsvr01.gel.com:7778/pls/lims/de_ref_material.decay_correction).

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14.4.5.8 The percent difference between the Calibrated Activity

and Measured Activity is calculated by the spreadsheet

and is displayed under the column marked Difference. The

verification is considered acceptable if all values in the

Difference column are less than 10%. If the Difference is

10% or greater, the verification is considered invalid and

must be performed again. If two verifications fail notify

Group Leader or Team Leader for further action.

14.5 Performance Checks

14.5.1 Daily Quality Control Calibration Check (QCC)

14.5.1.1 The QCC should be counted daily or prior to sample

counting. If no samples are being counted this check is not

required.

14.5.1.2 Load the QCC check source on the detector(s). If multiple

QCC checks are being started skip to step 14.5.1.5.

14.5.1.3 From the PROcount window, select QC Calibration

Check.

14.5.1.4 Select the detector and select OK.

14.5.1.5 To start multiple QCC checks at once, select QC Multi

Calibration Checks from the PROcount window.

14.5.1.6 Highlight each detector you wish to start by clicking once on

the detector name. Once you have highlighted all of the

detectors you wish to start, select OK.

14.5.2 Daily Quality Control Background Check (QCB)

14.5.2.1 The QCB should be counted daily or prior to sample

counting. If no samples are being counted this check is not

required.

14.5.2.2 Ensure the detector shield(s) are empty prior to running the

QCB. If multiple QCB checks are being started, skip to step

14.5.2.5.

14.5.2.3 From the PROcount window, select QC Background

Check.

14.5.2.4 Select the detector and select OK.

14.5.2.5 To start multiple QCB checks at once, select QC Multi

Background Checks from the PROcount window.

14.5.2.6 Highlight each detector you wish to start by clicking once

on the detector name. Once you have highlighted all of the


14.5.3 Weekly Environmental Background

14.5.3.1 Ensure the detector shield(s) is (are) empty. The same

process will be used to start single and multiple weekly

environmental background counts.

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14.5.3.2 Select Count Start MultipleBackgrounds from the

PROcount window.

14.5.3.3 highlight each detector you wish to start by clicking once

on the detector name. Once you have highlighted all of the


14.5.4 Generating the Daily and Weekly Check Reports

14.5.4.1 Daily check reports will generate every day following the

completion of the QCC and QCB counts for each detector

that will be in operation.

14.5.4.2 In the DECterm, type the command “@QA_REPORT D”

then hit ENTER.

14.5.4.3 Weekly check reports will be completed once per week,

typically Monday, following the completion of the weekly

background subtraction counts.

14.5.4.4 In the DECterm, type the command “@QA_REPORT B”

then hit ENTER.

15.0 PROCEDURE FOR ANALYSIS AND INSTRUMENT OPERATION

15.1 Prepare the sample as outlined in GL-RAD-A-013 for The Determination of

Gamma Isotopes.

15.2 Sample Counting

15.2.1 Prior to starting a sample count the detector used must be scanned into

AlphaLIMS. In a web browser, enter the following address:

http://prodsvr01.gel.com:7778/pls/lims/inst_instrument.start_count

15.2.2 Each sample and detector are labeled with a Universal Product Code

(UPC). First scan the UPC code for the detector and then scan the UPC

code for the sample. Continue doing so for any additional sample counts.

Once this has been done, select Submit on the web page.

15.2.3 Load the sample on the detector.

15.2.4 Select Count Start a Count from the ProCount Main Menu.

15.2.5 Select a detector and select OK.

15.2.6 Enter the batch to be started and select OK.

15.2.7 Select the sample to be counted.

15.2.8 Enter the sample specific information into the Sample Information screen

and select OK.

15.2.9 Select the Analysis Sequence file used for analysis and select OK.

15.2.10 Select the counting geometry and select OK.


Refer to GL-RAD-I-010 for Counting Room Instrumentation Maintenance.

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17.0 DATA RECORDING, CALCULATION AND REDUCTION METHODS

Data recording, calculation and reduction take place in accordance with GL-RAD-D-003

and GL-RAD-D-006.

18.0 POLLUTION/CONTAMINATION

Ensure all samples are bagged prior to counting to prevent instrument contamination.

19.0 DATA REVIEW, APPROVAL AND TRANSMITTAL

Refer to GL-RAD-D-003 for Data Review, Validation, and Data Package Assembly.

20.0 CORRECTIVE ACTION FOR OUT-OF-CONTROL OR UNACCEPTABLE DATA

Corrective action for out-of-control data might require instrument maintenance, re-

analysis, using a new spike mix, or a more complex set of actions. When trouble-

shooting measures (refer to Section 21) fail to bring an analytical process or data into

control, a data exception report and/or corrective action should be initiated in accordance

with GL-QS-E-004.

21.0 CONTINGENCIES FOR HANDLING THESE SITUATIONS

Troubleshooting the instrument is a function of analyst experience. In-house service is

obtained from GEL’s Group Leader or other qualified personnel. If vendor assistance is

needed, then the appropriate vendor is contacted. Maintenance logbooks are kept for

each instrument and contain entries for both routine and non-routine maintenance

procedures.


22.1 Each sample analysis that is performed is documented in the instrument run log in

accordance with GL-LB-E-009 for Run Logs.

22.2 All raw data printouts, calculation spreadsheets, and batch checklists are filed with

the sample data for archival in accordance with GL-RAD-D-003 for Data Review,

Validation, and Data Package Assembly.

22.3 Instrument maintenance is recorded in accordance with GL-LB-E-008 for Basic

Requirements for the Use and Maintenance of Laboratory Notebooks, Logbooks,

Forms and Other Recordkeeping Devices.

22.4 Records generated as a result of this procedure are maintained as quality

documents in accordance with GL-QS-E-008 for Quality Records Management

and Disposition.


Laboratory waste is disposed in accordance with the Laboratory Waste Management

Plan, GL-LB-G-001.

24.0 REFERENCES

24.1 United States Department of Energy, Environmental Measurements Laboratory,

HASL-300 The Procedures Manual of the Environmental Measurements

Laboratory, 28th

Edition, “Gamma Radioassay,” Ga-01-R (Vol. 1), February

1997.

24.2 United States Environmental Protection Agency, Prescribed Procedures for

Measurement of Radioactivity in Drinking Water, Method 901.1, August 1980.

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24.3 American National Standards Institute, American National Standard for

Calibration and Use of Germanium Spectrometers for the Measurement of

Gamma-Ray Emission Rates of Radionuclides, ANSI N42.14-1999.

24.4 Canberra Model 480720 ProCount-ESP Users Manual, September 2000.

24.5 Canberra Model 480726 Genie-ESP System Users Manual, September 2000.

24.6 Canberra Model 480198 Genie VMS Users Manual, 2000.

24.7 ASTM, International, Standard Practice for Setup, Calibration, and Quality

Control of Instruments Used for Radioactive Measurements, D7282-6, Nov. 2010.

25.0 HISTORY

Revision 15: Procedural updates made to SOP to reflect the process currently being used.

Revision 16: Added criteria for acceptance of FWHM calibration.

Revision 17: Updated sections 14.4.3.6 and 14.4.5.2 for clarification.

Revision 18: Added note to section 14.4 to clarify instrument calibration expiration dates.

Revision 19: Revised to include new GL-RAD-D-006 for calculations.

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DOCUMENT TITLE: METALS DIGESTION

REFERENCED METHOD: EPA 3050B

SOP ID: MET-3050B

REVISION NUMBER: 14


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TABLE OF CONTENTS

1.SCOPE AND APPLICATION ......................................................................................................................... 3 2.METHOD SUMMARY ................................................................................................................................... 3 3.DEFINITIONS ................................................................................................................................................ 3 4.INTERFERENCES .......................................................................................................................................... 4 5.SAFETY ......................................................................................................................................................... 4 6.SAMPLE COLLECTION, CONTAINERS, PRESERVATION AND STORAGE ............................................... 4 7.STANDARDS, REAGENTS, AND CONSUMABLE MATERIALS................................................................... 4 8.APPARATUS AND EQUIPMENT .................................................................................................................. 6 9.PREVENTIVE MAINTENANCE ..................................................................................................................... 6 10.RESPONSIBILITIES ...................................................................................................................................... 7 11.PROCEDURE .............................................................................................................................................. 7 12.QA/QC REQUIREMENTS........................................................................................................................... 9 13.DATA REDUCTION AND REPORTING ..................................................................................................... 9 14.CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA ......................... 10 15.METHOD PERFORMANCE ........................................................................................................................ 10 16.POLLUTION PREVENTION AND WASTE MANAGEMENT ...................................................................... 10 17.TRAINING .................................................................................................................................................. 11 18.METHOD MODIFICATIONS ...................................................................................................................... 11 19.REFERENCES .............................................................................................................................................. 11 20.CHANGES SINCE THE LAST REVISION .................................................................................................... 11

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METALS DIGESTION

1. SCOPE AND APPLICATION

1.1. This procedure uses techniques described in method 3050B for acid digestion of sediments,

sludges, and soil samples designated for “Total Metals” analysis. One technique is designed

for the preparation of samples for analysis by flame AA (Methods 7420-Pb, 7742-Se, and

7062-As) or ICP-OES (methods 6010 and 200.7). Another technique is given for the

preparation of samples for analysis by GFAA (see SOP MET-GFAA for methods) or ICP-MS

(methods 6020 and 200.8). This procedure is not a total digestion technique, but extracts

“environmentally available” elements from the sample of interest.

2. METHOD SUMMARY

2.1. One-gram equivalent dry weight sediment, sludge, or soil samples are digested with repeated

additions of nitric acid (HNO3) and hydrogen peroxide (H2O2). For GFAA and ICP-MS analysis

the resultant digestate is reduced in volume while heating and then diluted to a final volume

of 100 mL. For ICP-OES and flame AA analysis, hydrochloric acid (HCl) is added to the initial

digestate and the sample is refluxed prior to dilution to a final volume of 100 mL.

3. DEFINITIONS

3.1. - A batch of samples is a group of environmental samples that are prepared and/or

analyzed together as a unit with the same process and personnel using the same lot(s) of

reagents. It is the basic unit for analytical quality control.

3.2. - A preparation batch is composed of one to twenty field samples, all of the

same matrix, and with a maximum time between the start of processing of the first and last

samples in the batch to be 24 hours.

3.3.

3.3.1. Field Sample - An environmental sample collected and delivered to the laboratory for

analysis; a.k.a., client’s sample.

3.3.2. Laboratory Sample - A representative portion, aliquot, or subsample of a field sample

upon which laboratory analyses are made and results generated.

3.4. - The matrix of an environmental sample is distinguished by its

physical and/or chemical state and by the program for which the results are intended. The

following sections describe the matrix distinctions. These matrices shall be used for purpose of

batch and quality control requirements.

3.4.1. Solids - Any solid sample such as soil, sediment, sludge, and other materials with >15%

settleable solids.

3.5. - A laboratory blank that has been fortified with target

analyte and used to determine that the analysis is in control.

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3.6. - In the matrix spike analysis, predetermined quantities of target analytes

are added to a sample matrix prior to sample preparation and analysis. The percent recovery

is calculated. The MS is used to evaluate the effects of the sample matrix on the method used

for the analysis. The concentration of the spike should be at three to five times the sample

result or at levels specified by a project analysis plan.

3.7. - A laboratory duplicate. The duplicate sample is a separate field

sample aliquot that is processed in an identical manner as the sample proper. The relative

percent difference between the samples is calculated and used to assess analytical precision.

3.8. - The method blank is an artificial sample composed of analyte-free water

or solid matrix and is designed to monitor the introduction of artifacts into the analytical

process. The method blank is carried through the entire analytical procedure.

4. INTERFERENCES

4.1. Refer to the determinative method for a discussion of interferences.

5. SAFETY

5.1. All appropriate safety precautions for handling solvents, reagents and samples must be taken

when performing this procedure. This includes the use of personnel protective equipment,

such as, safety glasses, lab coat and the correct gloves.

5.2. Chemicals, reagents and standards must be handled as described in the ALS safety policies,

approved methods and in MSDSs where available. Refer to the ALS Environmental, Health and

Safety Manual and the appropriate MSDS prior to beginning this method.

5.3. Hydrochloric and/or Nitric Acid are used in this method. These acids are extremely corrosive

and care must be taken while handling them. A face shield must be used while pouring

concentrated acids. And safety glasses should be worn while working with the solutions. Lab

coat and gloves should always be worn while working with these solutions.

6. SAMPLE COLLECTION, CONTAINERS, PRESERVATION AND STORAGE

6.1. Samples may be collected in plastic or glass jars. Non-aqueous samples are refrigerated at 4

2°C from receipt until analysis.

6.2. The recommended holding time is 6 months from the day of sampling.

7. STANDARDS, REAGENTS, AND CONSUMABLE MATERIALS

7.1. Reagent grade chemicals shall be used in all tests. Other grades may be used, provided it is

first ascertained that the reagent is of sufficiently high purity to permit its use without

lowering the accuracy of the determination. The preparation for all laboratory prepared

reagents and solutions must be documented in a laboratory logbook. Refer to the SOP

Reagent/Standards Login and Tracking (ADM-RTL) for the complete procedure and

documentation requirements.

7.2. Reagent water: ASTM Type I water (resistivity >18 MΏ-cm, conductivity <0.056 uS/cm).

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7.3. Concentrated Nitric Acid: J.T. Baker “Instra-analyzed”, Trace Metals Grade

7.4. Concentrated Hydrochloric Acid: EMD GR ACS

7.5. Hydrogen Peroxide (30%): EMD GR ACS

7.6. Standards

7.6.1. Stock standards may be purchased from a number of vendors. All reference standards,

where possible, must be traceable to SI units or NIST certified reference materials. The

vendor assigned expiration date is used.

7.6.2. Metals spiking solutions: Five spiking solutions are needed to prepare the matrix spike

sample; SS1, SS2, SS3, SS4, and SS5.

7.6.3. Follow the formulations laid out on the “Metals Spike Form” (see attached Table A).

These solutions are prepared in acid rinsed Class A volumetric flasks using purchased

custom mixed standards or 1000 ppm single analyte standards. Aliquots are made

using acid rinsed Class A volumetric pipettes of the appropriate size.

7.6.4. SS1 ( Al, Ag, Ba, Be, Cd, Co, Cr, Cu, Fe, Pb, Mn, Ni, Sb, V, and Zn): Fill a 1000 mL

volumetric flask approximately half full with reagent water, add 50 mL of nitric acid

and mix. Next add 100 mL of the custom mixed standard (CAS-CAL-14) purchased

from “Inorganic Ventures”. In addition add 50 mL of 1000 ppm Antimony(use the

Antimony standard that does not contain HCL.) Dilute to volume with reagent water,

mix thoroughly and transfer to a 1000 mL Teflon bottle for storage. The solution

expiration date is determined by the earliest expiration date of any single component

in the solution.

7.6.5. SS2 (GFAA As, Cd, Cu, Pb, Se, Tl): Fill a 500 mL volumetric flask approximately half full

with reagent water, add 25 mL of nitric acid and mix. Next add 2.0 mL each of 1000

ppm Arsenic, Cadmium, Copper, Lead, Selenium, and Thallium. Dilute to volume with

reagent water, mix thoroughly and transfer to a 500 mL Teflon bottle for storage. The

solution expiration date is determined by the earliest expiration date of any single

component in the solution.

7.6.6. SS3 (As, Se, Tl, and Hg): Fill a 500 mL volumetric flask approximately half full with

reagent water, add 25 mL of nitric acid and mix. Next add 50 mL each of 1000 ppm

Arsenic, Selenium, and Thallium. Add 6.0mL of 1000ppm Hg. Dilute to volume with

reagent water, mix thoroughly and transfer to a 500 mL Teflon bottle for storage. The

solution expiration date is determined by the earliest expiration date of any single

component in the solution.

7.6.7. SS4 (B, Mo): Fill a 500 mL volumetric flask approximately half full with reagent water,

add 25 mL of nitric acid and mix. Next add 50 mL each of 1000 ppm Boron and

Molybdenum. Dilute to volume with reagent water, mix thoroughly and transfer to a

500 mL Teflon bottle for storage. The solution’s expiration date is determined by the

earliest expiration date of any single component in the solution.

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7.6.8. SS5 (K,Na,Mg,Ca): Fill a 200 mL volumetric flask approximately half full with reagent

water add 10.0 mL of nitric acid and mix. Next add 20 mL each of 10,000 ppm

Potassium, Sodium, Magnesium and Calcium. Dilute to volume with reagent water, mix

thoroughly and transfer to a 250 mL Teflon bottle for storage. The solution’s

expiration date is determined by the earliest expiration date of any single component

in the solution.

7.7. Metals reference material (ERA Priority PollutnT/CLP Inorganic Soil) for use as the laboratory

control sample. The expiration date is assigned by the manufacturer.

7.8. Teflon beads, Teflon boiling chips, or other suitable blank material.

8. APPARATUS AND EQUIPMENT

8.1. 125 mL plastic cup beaker cup, calibrated at 50mL and 100mL

8.2. Borosilicate watch glasses

8.3. Block Digester, calibrated to maintain 95°C ± 2°C

8.4. Hot Plates: “Thermolyne Cimerac 3”, calibrated to maintain 95°C ± 2°C

8.5. Laboratory balance, top-loader capable of reading 0.01g

8.6. Digestion tubes, 125 mL - Environmental Express. An accuracy and precision verification

check must be made with each new vendor lot prior to use. Refer to the SOP for Checking

Volumetric Labware ADM-VOLWARE, for further detailed instructions. Performance data must

meet the accuracy and precision requirements specified in Table 1 (ADM-VOLWARE) for non-

volumetric labware used for measuring initial and/or final digestate volumes.

8.7. USS # 10 sieve.

9. PREVENTIVE MAINTENANCE

9.1. All maintenance activities are recorded in a maintenance logbook. Pertinent information must

be in the logbook. Maintenance entries should include date, symptom of problem, corrective

actions, and description of maintenance, date, and name. The log should contain a reference

to return to analytical control.

9.2. Maintenance for this procedure is generally limited to glassware cleaning, pipet monitoring,

and hot plate calibration. Procedures for glassware washing are described in the SOP for

Metals Laboratory Glassware Cleaning (MET-GC). Procedures for pipet monitoring are given in

the SOP for Checking Volumetric Labware, (ADM-VOLWARE).

9.3. Each hotplate or block digester is uniquely identified and the temperature is verified with each

batch of samples. To perform the verification, a certified thermometer is placed in a container

half filled with mineral oil, which is then placed in the center of the hotplate or block digester.

The thermometer does not touch the bottom of the container. The temperature is turned to

the 95°C setting and the mineral oil is allowed to come to temperature. The analyst will verify

that the hotplate gives a temperature of 95°C ± 2°C. If not, the thermostat is adjusted until the

thermometer reads and maintains 95°C ± 2°C. The thermostat is then marked to clearly

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indicate the correct setting to be used during sample digestion (when using Hot Plates.). Each

hot Block has an assigned calibrated thermometer. The Temperature and the correction factor

of the assigned thermometer is recorded on the digestion bench sheet.

10. RESPONSIBILITIES

10.1. It is the responsibility of the analyst to perform the analysis according to this SOP and to

complete all documentation required for data review. Analysis and interpretation of the

results are performed by personnel in the laboratory who have demonstrated the ability to

generate acceptable results utilizing this SOP. This demonstration is in accordance with the

training program of the laboratory. Final review and sign-off of the data is performed by the

department supervisor/manager or designee.

10.2. It is the responsibility of the department supervisor/manager to document analyst training.

11. PROCEDURE

11.1. Record all digestion and sample information on the applicable benchsheet.

11.2. Mix the sample thoroughly to achieve homogeneity. Sieve if necessary using a USS #10

sieve.

11.3. It can be difficult to obtain a representative sample with wet or damp materials. As per

Method 3050B, wet samples may be dried, crushed, and ground to reduce subsample

variability, however, drying is not recommended since drying may affect the extraction of

the analytes of interest in the sample.

11.4. Weigh approximately 1g of sample into a 125ml plastic beaker cup and record the weight

to the nearest 0.01g. For sludge’s and sediments that have high moisture content, use

more sample. A plastic 10.0 mL disposable pipette is used to measure 10.0 mL of sample.

The volume and weight of the pipetted sample is recorded. In cases where the sludge is

very thick a 10.0 mL graduated cylinder may be used. The objective is to use about 1g of

dry weight sample. For analysis of Lead by Flame AA, use about 2.5g of dry wt. sample

and change the final dilution volume to 50ml. This will achieve a lower detection limit

needed for most projects. At this point add the appropriate spiking solutions directly

onto the designated spike sample prior to addition of reagents.

11.5. Add 5ml reagent water and 5ml concentrated HNO3

. Place in a hot block, cover and reflux

(without boiling) at 95ºC for 10 to 15 minutes. Allow the sample to cool. Add 5ml of

concentrated HNO3

, cover and reflux for 30 minutes. If brown fumes are generated,

indicating oxidation of the sample by HNO3

, repeat the addition of 5ml of HNO3

and reflux

over and over until no brown fumes are given off. Reduce the digestate volume to

approximately 5 mL without boiling or digest for two hours maintaining a covering of

solution over the bottom of the beaker at all times. If this occurs discard the digestate

and begin with a new sample aliquot.

The 95°C hot block temperature must be monitored and documented on a per-batch

basis. The actual measured temperature, thermometer correction factor, and corrected

temperature must all be recorded.

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All Wisconsin samples must digest for 2 hours after generation of brown fumes has

ceased.

11.6. Cool the sample and add 3 mL of 30% H2

O2

. Cover and heat to start the peroxide

reaction. Care must be taken to ensure that losses do not occur due to excessive

effervescence. Heat in the hot block until effervescence subsides. Remove from hot

block and cool the beaker.

11.7. Continue to add 30% H2

O2

in 3ml aliquots with warming until the effervescence is

minimal, or until the general sample appearance is unchanged. Do not add more than

10ml of 30% H2

O2

. When the peroxide additions are complete cover the sample with a

watch glass and continue heating the acid-peroxide digestate until the volume has been

reduced to approximately 5 mL or heat at 95°± 5°C without boiling for 2 hours. Do not let

the samples go to dryness, by ensuring the solution covers the bottom of the vessel at all

times.

: All Wisconsin samples must digest for 2 hours after the final peroxide addition.

If the sample is being prepared for analysis by ICP-OES or Flame AA, add 10 mL of

concentrated HCl. If the sample is being prepared for ICP-MS or GFAA analysis no HCl is

added. Dilute the sample to 100 mL with reagent water: ASTM Type I water (resistivity >18

MΩ-cm, conductivity <0.056 uS/cm) in a 125 mL plastic beaker cup.

For method 7062 and 7742 samples, the 3050B soil digestion is modified as follows:

After the final peroxide addition (i.e. before the final reduction stage) add 5.0mL of

concentrated hydrochloric acid and reduce the digestate volume to less than 5.0mL, but not to

dryness. After cooling, dilute the digestate to 100mL with reagent water.

11.8. Cover and reflux the Flame AA and ICP samples for 15 minutes at 95o

C. After cooling, the

samples may be diluted to 100ml for ICP analysis, or 50ml for Flame AA analysis.

11.9. Particulates in the digestates that may clog the nebulizer are allowed to settle overnight,

or the digestates may be centrifuged.

11.10. To improve the solubility for Antimony, Barium, Lead and Silver, the following

modification of the digestion procedure may be used as directed by the client or project

chemist.

11.10.1.Weigh (to the nearest 0.01g) 1.00 g of sample into a 125ml plastic cup. For

sludges and sediments that have high moisture content, use more sample. The

objective is to use about 1g of dry weight sample.

11.10.2.Add 2.5mL HNO3

and 10mL HCl and cover with a watch glass. Reflux for 15

minutes.

11.10.3.Filter the digestate through Whatman No. 41or equivalent filter paper and collect

in a 100mL volumetric flask. Wash the filter paper, while still in the funnel, with

no more than 5mL of hot (95°) HCl, and then with 20mL of hot (95°) reagent water.

Collect washing in the same volumetric flask.

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11.10.4.Remove the filter and residue from the funnel, and place them back in the beaker.

Add 5mL HCl, cover and heat at 95° ± 5° until the filter paper dissolves. Remove

from the heat and wash the cover and sides with reagent water.

11.10.5.Filter the residue and collect the filtrate in the same 100mL flask. Allow to cool,

then dilute to volume.

11.10.6.If precipitation occurs in the flask upon cooling, do not dilute to volume. Instead,

add up to 10mL of HCl to dissolve the precipitate. After precipitate is dissolved,

dilute to volume with water.

12. QA/QC REQUIREMENTS

12.1. Initial Precision and Recovery Validation

12.1.1. The accuracy and precision of the procedure must be validated before analyses of

samples begin, or whenever significant changes to the procedures have been made.

To do this, four blank matrix samples are spiked with the LCS spike solution, then

prepared and analyzed.

12.2. Monitor Hot Blocks and Hotplates on a per batch basis. Report all deficiencies to the Lab

Manager. Corrective action must be taken.

12.3. Digest one laboratory control sample with each batch. Weigh 1.00 g of the current lot of

Environmental Resource Associates PriorityPollutnT/CLP Inorganic Soil prepared reference

material into a 150 mL beaker and digest as per the procedure.

12.4. Digest one preparation blank (method blank) per digestion batch, or per 20 samples whichever

is more frequent. For the method blank, use Teflon beads, Teflon boiling chips, or other

suitable solid blank material and follow the digestion procedures.

12.5. Digest one duplicate and one spiked sample with each sample matrix. Prepare one duplicate

and spike sample per each digestion batch, or per twenty samples whichever is more frequent.

At times, specific samples will be assigned as duplicates of spikes depending on client

requirements.

12.6. Soil spikes for ICP and ICP-MS are prepared by adding 2.0 mL of SS1, and 1.0 mL of SS3, SS4

and SS5 directly to the sample aliquot, prior to the addition of any water or acid. Fill out a

spiking data sheet and keep it with the digestion data sheets.

12.6.1. For GFAA digestions 2.0 mL of SS2 is added to the sample aliquot designated as the

matrix spike sample. The matrix spike sample is then digested as per the procedure.

13. DATA REDUCTION AND REPORTING

13.1. Digestion data sheets including weights and volumes used and reagents/acids are completed

and a prep run number or batch lot number is assigned and attached to the data sheet. The

lot numbers for the reagents used are added to the digestion data sheet (see Attachments).

13.2. Spiking sheets are included (See Attachments).

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13.3. Data Review and Assessment

13.3.1. Refer to the SOP for Laboratory Data Review Process for general instructions for data

review.

13.3.2. It is the supervisor’s responsibility to ensure that digestions data is reviewed to ensure

that all quality control requirements have been met and documentation is complete.

14. CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA

14.1. Refer to the SOP for Nonconformity and Corrective Action (CE-QA008) for procedures for

corrective action. Personnel at all levels and positions in the laboratory are to be alert to

identifying problems and nonconformities when errors, deficiencies, or out-of-control

situations are detected.

14.2. Handling out-of-control or unacceptable data

14.2.1. On-the-spot corrective actions that are routinely made by analysts and result in

acceptable analyses should be documented as normal operating procedures, and no

specific documentation need be made other than notations in laboratory maintenance

logbooks, runlogs, for example.

14.2.2. Some examples when documentation of a nonconformity is required using a

Nonconformity and Corrective Action Report (NCAR):

Quality control results outside acceptance limits for accuracy and precision

Method blanks or continuing calibration blanks (CCBs) with target analytes above

acceptable levels

Sample holding time missed due to laboratory error or operations

Deviations from SOPs or project requirements

Laboratory analysis errors impacting sample or QC results

Miscellaneous laboratory errors (spilled sample, incorrect spiking, etc.)

Sample preservation or handling discrepancies due to laboratory or operations

error

15. METHOD PERFORMANCE

15.1. This method was validated through single laboratory studies of accuracy and precision. Refer

to the reference method for additional method performance data available.

15.2. The method detection limit (MDL) is established using the procedure described in the SOP CE-

QA011, Performing Method Detection Limit Studies and Establishing Limits of Detection and

Quantification. Method Reporting Limits are established for this method based on MDL

studies and as specified in the ALS Quality Assurance Manual.

16. POLLUTION PREVENTION AND WASTE MANAGEMENT

16.1. It is the laboratory’s practice to minimize the amount of solvents, acids, and reagents used to

perform this method wherever feasibly possible. Standards are prepared in volumes

consistent with methodology and only the amount needed for routine laboratory use is kept

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on site. The threat to the environment from solvents and/or reagents used in this method can

be minimized when recycled or disposed of properly.

16.2. The laboratory will comply with all Federal, State, and local regulations governing waste

management, particularly the hazardous waste identification rules and land disposal

restrictions as specified in the ALS Environmental Health and Safety Manual.

16.3. This method uses acid. Waste acid is hazardous to the sewer system and to the environment.

All acid waste must be neutralized to a pH of 2.5-12 prior to disposal down the drain. The

neutralization step is considered hazardous waste treatment and must be documented on the

treatment by generator record. See the ALS EH&S Manual for details.

17. TRAINING

17.1. Training outline

17.1.1. Review literature (see references section). Read and understand the SOP. Also review

the applicable MSDS for all reagents and standards used. Following these reviews,

observe the procedure as performed by an experienced analyst at least three times.

17.1.2. The next training step is to assist in the procedure under the guidance of an

experienced analyst. During this period, the analyst is expected to transition from a

role of assisting, to performing the procedure with minimal oversight from an

experienced analyst.

17.1.3. Perform initial precision and recovery (IPR) study as described above for water samples.

Summaries of the IPR are reviewed and signed by the supervisor. Copies may be

forwarded to the employee’s training file. For applicable tests, IPR studies should be

performed in order to be equivalent to NELAC’s Initial Demonstration of Capability.

17.2. Training is documented following the SOP ADM-TRAIN.

NOTE: When the analyst training is documented by the supervisor on internal training

documentation forms, the supervisor is acknowledging that the analyst has read and

understands this SOP and that adequate training has been given to the analyst to competently

perform the analysis independently.

18. METHOD MODIFICATIONS

18.1. The method uses 2 mL of water and 3 mL of H202 in step 11.6. The lab does not add the 2

mL of water. 3.0 mL aliquots of 30% H202 in lieu of 1.0 mL aliquots are added subsequently.

19. REFERENCES

19.1. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods. EPA SW-846, 3rd Edition,

Final Update III, Method 3050B, December 1996.

19.2. Table A METALS SPIKING SOLUTIONS CONCENTRATIONS FORM

20. CHANGES SINCE THE LAST REVISION

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20.1. Reformatted SOP to current ALS format and style.

20.2. Updated internal SOP references.

20.3. Few minor changes (correct typos and errors, etc.).

20.4. Section 7.6.6 – revised to include Mercury in SS3 solution.

20.5. Section 8.6 – revised to update tubes to those in use.

20.6. Section 11.5 – Added second note regarding Wisconsin samples.

20.7. Section 11.7 – Inserted first note regarding Wisconsin samples.

20.8. Section 12.6 – revised to list spiking with current solution formulations.

20.9. Section 13.3 – New section.

20.10. Section 14 – updated to current standard language for the section.



20.13. Table A – updated

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Solution mL of 1000ppm Final Solution Enter ml

Name Element Solution Volume Conc. mg/L Added

HNO3 50.0 1000ml -

Al 100* 1000ml 200

Ag 100* 1000ml 5

Ba 100* 1000ml 100

Be 100* 1000ml 5

Cd 100* 1000ml 5

Co 100* 1000ml 50

K-MET SS1 Cr 100* 1000ml 20

Cu 100* 1000ml 25

Fe 100* 1000ml 100

Pb 100* 1000ml 50

*** Add after HNO3 Mn 100* 1000ml 50

and before cas cal Ni 100* 1000ml 50

-14 Sb*** 50 1000ml 50

when making the V 100* 1000ml 50

solution Zn 100* 1000ml 50

HNO3 25.0 500ml -

K-MET SS2 As 2.0 500ml 4

Cd 2.0 500ml 4

Pb 2.0 500ml 4

Se 2.0 500ml 4

Tl 2.0 500ml 4

Cu 2.0 500ml 4

K-MET SS3 HNO3 25.0 500ml -

As 50.0 500ml 100

Se 50.0 500ml 100

Tl 50.0 500ml 100

Hg 6 500ml 12

HNO3 25 500ml -

K-MET SS4 B 50 500ml 100

Mo 50 500ml 100

K-MET SS5 HNO3 10.0 200ml -

K** 20 200ml 1000

Na** 20 200ml 1000

Mg** 20 200ml 1000

Ca** 20 200ml 1000

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K-MET

GFLCSW HNO3 10.0 1000ml -

As, Pb, Se, Tl 5.0 1000ml 2.5

Cd - - 1.25

Cu 2.5 1000ml 2.5 K-MET QCP-

CICV-1 Ca, Mg, Na, K no dilution - 2500

Al, Ba no dilution - 1000

Fe no dilution - 500

Co, Mn, Ni, V,

Zn no dilution - 250

Cu, Ag no dilution - 125

Cr no dilution - 100

Be no dilution - 25 K-MET QCP-

CICV-2 Sb no dilution - 500

K-MET QCP-

CICV-3 As, Pb, Se, Tl no dilution - 500

Cd no dilution - 250

* Denotes volume of mixed stock standard.

** Denotes 10,000 ppm individual stock standards.

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DOCUMENT TITLE: DETERMINATION OF METALS AND TRACE ELEMENTS

BY INDUCTIVELY COUPLED PLASMA-MASS

SPECTROMETRY (METHOD 6020)

REFERENCED METHOD: EPA 6020, 6020A

SOP ID: MET-6020

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TABLE OF CONTENTS

1.SCOPE AND APPLICATION ......................................................................................................................... 3 2.METHOD SUMMARY ................................................................................................................................... 3 3.DEFINITIONS ................................................................................................................................................ 3 4.INTERFERENCES .......................................................................................................................................... 5 5.SAFETY ......................................................................................................................................................... 6 6.SAMPLE COLLECTION, CONTAINERS, PRESERVATION AND STORAGE ............................................... 6 7.STANDARDS, REAGENTS, AND CONSUMABLE MATERIALS................................................................... 6 8.APPARATUS AND EQUIPMENT .................................................................................................................. 9 9.PREVENTIVE MAINTENANCE ..................................................................................................................... 9 10.RESPONSIBILITIES ...................................................................................................................................... 10 11.PROCEDURE .............................................................................................................................................. 10 12.QA/QC REQUIREMENTS........................................................................................................................... 12 13.DATA REDUCTION AND REPORTING ..................................................................................................... 16 14.CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA ......................... 17 15.METHOD PERFORMANCE ........................................................................................................................ 18 16.POLLUTION PREVENTION AND WASTE MANAGEMENT ...................................................................... 18 17.TRAINING .................................................................................................................................................. 18 18.METHOD MODIFICATIONS ...................................................................................................................... 19 19.REFERENCES .............................................................................................................................................. 19 20.CHANGES SINCE THE LAST REVISION .................................................................................................... 19

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DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA-

MASS SPECTROMETRY (METHOD 6020)


1.1. This procedure is used to determine the concentrations of certain elements in water, soil,

tissues, aqueous and non-aqueous wastes, and sediment samples using EPA Method 6020 or

6020A. Table 1 indicates analytes that are typically determined by this procedure and lists the

standard Method Reporting Limits (MRLs) for each analyte in water and soil. Project-specific

MRLs may apply, and if lower than standard MRLs, it is demonstrated through method

detection limit determinations and analysis of MRL standards that the MRL is achievable.

Method Detection Limits (MDLs) that have been achieved are listed in Table 1. These may

change as new studies are performed.

1.2. The complexity of the technique generally requires outside study of appropriate literature as

well as specialized training by a qualified spectroscopist. The scope of this document does not

allow for the in-depth descriptions of the relevant spectroscopic principles required for gaining

a complete level of competence in this scientific discipline.

2. METHOD SUMMARY

2.1. Prior to analysis, samples must be digested using appropriate sample preparation methods.

The digestate is analyzed for the elements of interest using ICP-mass spectrometry (ICP-MS).

2.2. Methods 6020 and 6020A describe the multi-elemental determination of analytes by ICP-MS.

The method measures ions produced by a radio-frequency inductively coupled plasma. Analyte

species originating in a liquid are nebulized and the resulting aerosol transported by argon gas

into the plasma torch. The ions produced are entrained in the plasma gas and introduced, by

means of an interface, into a mass spectrometer. The ions produced in the plasma are sorted

according to their mass-to-charge ratios and quantified with a channel electron multiplier.

Interferences must be assessed and valid corrections applied or the data flagged to indicate

problems. Interference correction must include compensation for background ions contributed

by the plasma gas, reagents, and constituents of the sample matrix.

3. DEFINITIONS




3.1.1. Preparation Batch - A preparation batch is composed of one to twenty field samples, all

of the same matrix, and with a maximum time between the start of processing of the

first and last samples in the batch to be 24 hours.

3.1.2. Analysis Batch - Samples are analyzed in a set referred to as an analysis sequence. The

sequence begins with instrument calibration (initial or continuing verification) followed

by sample extracts interspersed with calibration standards (CCBs, CCVs, etc.) The

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sequence ends when the set of samples has been analyzed or when qualitative and/or

quantitative QC criteria indicate an out-of-control situation.

3.2.









3.3.1. Aqueous - Any groundwater sample, surface water sample, effluent sample, and TCLP

or other extract. Specifically excluded are samples of the drinking water matrix and the

saline/estuarine water matrix.

3.3.2. Drinking water - Any aqueous sample that has been designated a potable or potential

potable water source.

3.3.3. Saline/Estuarine water - Any aqueous sample from an ocean or estuary or other salt-

water source.

3.3.4. Nonaqueous Liquid - Any organic liquid with <15% settleable solids.

3.3.5. Animal tissue - Any tissue sample of an animal, invertebrate, marine organism, or other

origin; such as fish tissue/organs, shellfish, worms, or animal material.


settleable solids.

3.3.7. Chemical waste - Any sample of a product or by-product of an industrial process that

results in a matrix not described in one of the matrices in Sections 3.4.1 through 3.4.6.

These can be such matrices as non-aqueous liquids, solvents, oil, etc.

3.3.8. Miscellaneous matrices – Samples of any composition not listed in 3.4.1 – 3.4.7. These

can be such matrices as plant material, paper/paperboard, wood, auto fluff, mechanical

parts, filters, wipes, etc. Such samples shall be batched/grouped according to their

specific matrix.

3.4. Matrix Spike/Duplicate Matrix Spike (MS/DMS) Analysis - In the matrix spike analysis,

predetermined quantities of target analytes are added to a sample matrix prior to sample

preparation and analysis. The purpose of the matrix spike is to evaluate the effects of the

sample matrix on the method used for the analysis. Duplicate samples are spiked, and

analyzed as a MS/DMS pair. Percent recoveries are calculated for each of the analytes

detected. The relative percent difference (RPD) between the duplicate spikes (or samples) is

calculated and used to assess analytical precision. The concentration of the spike should be at

the midpoint of the calibration range or at levels specified by a project analysis plan.

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3.5. Laboratory Duplicates (DUP) – Duplicates are additional replicates of samples that are

subjected to the same preparation and analytical scheme as the original sample. The relative

percent difference (RPD) between the sample and its duplicate is calculated and used to assess

analytical precision.

3.6. Surrogate - Surrogates are organic compounds which are similar to analytes of interest in

chemical composition, extraction and chromatography, but which are not normally found in

environmental samples. The purpose of the surrogates is to evaluate the preparation and

analysis of samples. These compounds are spiked into all blanks, standards, samples and

spiked samples prior to extraction and analysis. Percent recoveries are calculated for each

surrogate.

3.7. Method Blank (MB) - The method blank is an artificial sample composed of analyte-free water



3.8. Laboratory Control Samples (LCS) – The LCS is an aliquot of analyte free water or analyte free

solid to which known amounts target analytes are added. The LCS is prepared and analyzed in

exactly the same manner as the samples. The percent recovery is compared to established

limits and assists in determining whether the batch is in control.

3.9. Independent Verification Standard (ICV) - A pre-mixed, purchased, second-source standard

analyzed after the calibration curve. This is used to verify the validity of the initial calibration

standards

3.10. Continuing Calibration Verification Standard (CCV) - A mid-level standard analyzed at specified

intervals. Used to verify that the initial calibration curve is still valid for quantitative purposes.

3.11. Duplicates and Duplicate Matrix Spikes are additional replicates of samples that are subjected

to the same preparation and analytical scheme as the original sample. Depending on the

method of analysis, either a duplicate analysis (and/or a matrix spiked sample) or a matrix

spiked sample and duplicate matrix spiked sample (MS/DMS) are analyzed.

3.12. Standard Reference Material (SRM) – A material with specific certification criteria and is issued

with a certificate or certificate of analysis that reports the results of its characterizations and

provides information regarding the appropriate use(s) of the material. An SRM is prepared and

used for three main purposes: (1) to help develop accurate methods of analysis; (2) to calibrate

measurement systems used to facilitate exchange of goods, institute quality control,

determine performance characteristics, or measure a property at the state-of-the-art limit; and

(3) to ensure the long-term adequacy and integrity of measurement quality assurance

programs.

4. INTERFERENCES

4.1. Isobaric elemental interferences in ICP-MS are caused by isotopes of different elements

forming atomic ions with the same nominal mass-to-charge ratio (m/z). A data system must be

used to correct for these interferences. This involves determining the signal for another

isotope of the interfering element and subtracting the appropriate signal from the analyte

isotope signal. Attention should be given to circumstances where very high ion currents at

adjacent masses may contribute to ion signals at the mass of interest. Matrices exhibiting a

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significant problem of this type may require resolution improvement, matrix separation, or

analysis using another isotope.

4.2. Isobaric molecular and doubly-charged ion interferences in ICP-MS are caused by ions

consisting of more than one atom or charge, respectively. Most isobaric interferences that

could affect ICP-MS determinations have been identified in the literature. Refer to Method

6020/A for further discussion.

5. SAFETY

5.1. All appropriate safety precautions for handling solvents, reagents and samples must be taken

when performing this procedure. This includes the use of personnel protective equipment,

such as, safety glasses, lab coat and the correct gloves.




5.3. Hydrochloric and/or Nitric Acid are used in this method. These acids are extremely corrosive

and care must be taken while handling them. A face shield should be used while pouring acids.

And safety glasses should be worn while working with the solutions. Lab coat and gloves

should always be worn while working with these solutions.

5.4. High Voltage - The RF generator supplies up to 2000 watts to maintain an ICP. The power is

transferred through the load coil located in the torch box. Contact with the load coil while

generator is in operation will likely result in death. When performing maintenance on the RF

generator, appropriate grounding of all HV capacitors must be performed as per manufacturer.

5.5. UV Light - The plasma is an intense source of UV emission, and must not be viewed with the

naked eye. Protective lenses are in place on the instrument. Glasses with special protective

lenses are available when direct viewing of the plasma is necessary.


6.1. Aqueous samples are typically collected in plastic containers. Aqueous samples are preserved

with nitric acid (pH<2), then refrigerated at 4 2°C from receipt until digestion. Soil or solid

samples may be collected in plastic or glass jars. Non-aqueous samples are refrigerated at 4

2°C from receipt until digestion.

6.2. Samples are prepared via procedures in SOPs MET-DIG, MET-3020A, or MET-3050 depending

on matrix and project specifications.

6.3. Digestates are stored in the appropriate volumetric containers. Following analysis, digestates

are stored until all results have been reviewed. Digestates are neutralized prior to disposal

through the sewer system, 2 weeks after data is reviewed.


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7.1. All standards are prepared from NIST traceable standards. The expiration dates are assigned

according to the EPA method and the vendor’s assigned expiration dates. For example,

working ICS solutions are prepared weekly in accordance with Method 6020, Section 5.6.1.

7.1.1. 1000 ppm Single Element Stock Standard Solutions: Each stock standard is store at

room temperature on shelves located in room 113 of the metals lab. The

manufacturer, lot number, and expiration date of each stock standard is recorded in a

bound logbook also located in room 113. Additionally each stock standard is given a

unique, identifying name.

7.1.2. Intermediate Standard Solutions: Intermediate mixed stock solutions are made from

the individual stock standards described above. The individual component of each

mixed solution is recorded in a bound logbook located in the ICP-MS laboratory and

mixed solution is given a unique, identifying name. The expiration date for the

intermediate standard is the earlier of any one of its stock components.

7.1.3. Calibration Standards: Calibration standards are made fresh daily from the

intermediate standard solutions. Each individual intermediate standard used in the

calibration standard is recorded in a bound logbook located in the ICP-MS laboratory,

and the calibration standard solution is given a unique, identifying name. The

calibration standards unique name is used on the raw data to link the data to the

subsequent prepared standards and ultimately the original purchased stock standard.

7.2. Standards Preparation

7.2.1. Expiration of all standard solutions defaults to the earliest expiration date of an

individual component unless otherwise specified.

7.2.2. Calibration Standards

The calibration standard is prepared from two intermediate stock solutions. These

solutions are prepared in acid rinsed 1000 mL Class A volumetric flasks following the

formulations laid out on the attached example standard sheet (see Attachments). The

working calibration standard is made daily by aliquoting 2.5 mL of each of the

intermediate solutions in to a 100 mL Class A volumetric flask and diluting to volume

with 1% HNO3. This standard is also used as the Continuing Calibration Verification

(CCV).

7.2.3. Initial Calibration Verification (ICV)

7.2.3.1. The ICV intermediate stock solution is prepared in an acid rinsed 100 mL Class

A volumetric flask. The solution is prepared by adding 2.0 mL of Inorganic

Ventures QCP-CICV-1, 1.0 mL each of QCP-CICV-2 and QCP-CICV-3, 0.5 mL of

1000 ppm Molybdenum stock solution, 0.5 mL of 1000 ppm Uranium stock

solution, and 0.5mL of 1000ppm B, Bi, Sr, Ti solution and diluting to volume

with 1% HNO3.

7.2.3.2. The working ICV solution is prepared by aliquoting 0.5 mL of the mixed ICV

intermediate solution into an acid rinsed 100 mL Class A volumetric flask and

diluting to volume with 1% HNO3.

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: The ICV solution is not at the midpoint of the linear range which may

be as high as 1000 µg/L for some elements. The ICV solution used is a

premixed standard purchased from Inorganic Ventures and contains the

elements of interest between 2.5 and 100 µg/L. This solution provides

calibration confirmation at more representative levels, given that most ICP-MS

analyses are quantifying analytes in the low-ppb to sub-ppb range.

7.2.4. Interference Check Solutions (ICSA and ICSAB)

7.2.4.1. The ICSA is prepared in an acid rinsed 50 mL Class B volumetric flask by

aliquoting 1.0 mL of Elements ICSAm (CS-CAK02) solution and diluting to

volume with 1% HNO3.

7.2.4.2. The ICSAB is prepared in an acid rinsed 50 mL Class B volumetric flask by

aliquoting 1.0 mL of Elements ICSAm (CS-CAK02), 0.125 mL of Inorganic

Ventures 6020ICS-9B, and 0.250 mL of 10 ppm Molybdenum solutions and

diluting to volume with 1% HNO3.

7.2.5. Post-digestion spikes are performed by adding appropriate amounts of the calibration

intermediate solutions to aliquots of the sample digestate. The volumes of each

standard used vary based on the native concentrations found in the field samples.

Refer to the post-digestion spike in Section 12 for details.

7.2.6. Refer to the appropriate digestion SOP for details of LCSW and matrix spike solution

composition and preparation.

7.2.7. Tuning / Mass Calibration Solution

7.2.7.1. A 1ppm intermediate solution containing Be, Bi, Ce, Co, In, Li, Pb, Mg, and U is

prepared by adding 1.0 mL of each from 1000 ppm stock standards to an acid

rinsed 1000 mL volumetric flask and diluting to volume with 1% nitric acid.

The expiration date for the intermediate solution is the earliest of any one of

its stock components.

7.2.7.2. The working solution is prepared in three ways:

For the Agilent: a 1.0 ppb tune/mass calibration solution is prepared by

adding 1.0 mL of intermediate solution to an acid rinsed 1000 mL

volumetric flask and diluting to volume with 1% nitric acid.

For the X-Series (K-ICP-MS-03) instrument a 5.0 ppb tune/mass calibration

solution is prepared by adding 5.0 mL of intermediate solution to an acid


For the NexION (K-ICP-MS-04) instrument a 2.0 ppb tune/mass calibration

solution is prepared by adding 2.0 mL of intermediate solution to an acid


The expiration date for this solution is taken from the intermediate stock

above.

7.3. Internal Standards Stock Solution – Prepare solutions by adding appropriate amounts of each

1000 ppm single element stock solution to a acid rinsed 1000 mL volumetric flask and

diluting to volume with 1% nitric. Use this solution for addition to blanks, calibration standards

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and samples at a ratio of 0.5 mL of internal standard to 100 mL of solution, or dilute by an

appropriate amount using 1% (v/v) nitric acid, if the internal standards are being added by

peristaltic pump. The typical solutions are:

XSeries instrument: 50ppb Li; 25ppb Sc, Ga, Y; 10ppb Rh, In, Lu, Tm, Th.

Agilent instrument: 2ppm Li, Sc, Y, Ga, Ge, Ce, Tm, In, Lu, Th

NexION instrument: 30ppb In, Tm, Lu, Th; 60ppb Li, Rh, Au; 75ppb Sc;

100ppb Ga,Y; 500ppb Ge

7.4. Additional Reagents

7.4.1. Reagent water, ASTM Type II

7.4.2. “OmniTrace Ultra” Concentrated Nitric Acid (EM Science # NX0408-2)

7.4.3. Argon (Airgas Industrial Grade – 99.999% pure, bulk delivered)


8.1. ICP/MS instruments:

8.1.1. Instrument: Thermo Electron X-Series

Nebulizer: Conikal

Spray Chamber: VG Peltier-cooled

Cones: Nickel Sampler (1.0 mm orifice)

Nickel Skimmer (0.75 mm orifice)

8.1.2. Instrument: NexION 300D

Nebulizer: PFA-ST MIcroflow

Spray Chamber: Cyclonic, Peltier-cooled



8.1.3. Instrument: Agilent 7700

Nebulizer: MicroMist

Spray Chamber: Double Pass quartz spray chamber




9.1. All maintenance is documented in the instrument logbook. ALS/Kelso maintains a service

contract with the instrument manufacturer that allows for an unlimited number of service calls

and full reimbursement of all parts and labor.

9.2. Most routine maintenance and troubleshooting is performed by ALS staff. Preventive

maintenance activities listed below should be performed when needed as determined by

instrument performance (i.e. stability, sensitivity, etc.) or by visual inspection. Other

maintenance or repairs may, or may not require factory service, depending on the nature of

the task.

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cone removal and cleaning

removal and cleaning of ICP glassware and fittings

checking and cleaning RF contact strips

checking air filters and cleaning if necessary

checking the oil mist filters and cleaning if necessary

checking the rotary pump oil and adding or changing if necessary

removal and cleaning of extraction lens

removal and cleaning of ion lens stack

replace the electron multiplier as necessary









Documenting method proficiency, as described in the SOP for Documentation of Training, is

also the responsibility of the department supervisor/manager.

11. PROCEDURE

11.1. Refer to method 6020 (or 6020A) and the instrument manuals for detailed instruction on

implementation of the following daily procedures preceding an analytical run.

11.2. After the instrument has been placed in the "Operate" mode, begin completing the daily

instrument log (see Attachments). Refer to the instrument manuals for the optimum settings

for each instrument.

11.3. The following parameters are monitored to assure awareness of changes in the

instrumentation that serve as signals that optimum performance is not being achieved, or as

indicators of the physical condition of certain consumable components (i.e. EMT and cones).

11.3.1. Multiplier Voltages

11.3.2. Gas Flows - Coolant Ar

11.3.3. The nebulizer and auxiliary flows are adjusted later as part of the optimizing

procedure.

11.4. Optimization

11.4.1. Gas Flows

11.4.1.1.Allow a period of not less than 30 minutes for the instrument to warm up.

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11.4.1.2.Aspirate a mixed tune solution into the plasma and monitor the instrument

output signal of In at mass 115 on the ratemeter. Adjust the nebulizer and

auxiliary flows to obtain maximum signal. Adjust the tension screw on the

peristaltic pump to obtain minimum noise in the analytical signal. Record flow

rates and note any large variances.

Note: Significant differences in flow rates will be observed for different torches and

cones.

11.4.2. Tuning

11.4.2.1.Ion Lens Setting - While monitoring the output signal of a mixed tune solution

at mass 115 on the ratemeter, adjust the ion lenses to obtain maximum

sensitivity. Refer to the instrument manual for details on performing the

adjustments.

11.4.2.2.Mass Calibration - Aspirate the tune / mass calibration solution described in

section 7.2 and perform the mass calibration using the instrument’s Mass

Calibration program. (Refer to the instrument manual for details pertaining to

the mass calibration procedure.) The acceptance criteria for the mass

calibration is <0.1 amu from the true value. If the mass calibration fails criteria

re-tune the instrument and perform the mass calibration procedure again.

11.4.2.3.Resolution Check - Using the spectra created during the mass calibration

procedure; perform the resolution check to assure the resolution is less than

0.9 AMU at 5% peak height. If the resolution does not pass criteria adjust the

instrument’s resolution settings, run a new scan of the mass calibration

solution and recheck.

11.4.2.4.Stability Check - Using the tune / mass calibration solution, perform a short-

term stability check as per EPA Method 6020 or 6020A. The relative standard

deviations of five scans for each element in the tune solution must be < 5%. If

the test does not pass criteria determine the cause (i.e. dirty cones, improper

tune, etc.) correct the problem and re-run the test.

11.5. Analytical Run

11.5.1. Calibrate the instrument using a calibration blank (Standard 0), composed of reagent

water and 1% nitric acid, and the working calibration standard (8.2.2). The masses

typically monitored and those used for quantification are listed in Table 2. These

masses are set as defaults in the instrument’s analytical procedures. To begin select

the correct method. Nebulize Standard 0 (Blank) into the plasma. Allow 1-2 minutes

for system to equilibrate prior to establishing baseline. Follow directions on computer

screen to perform standardization. Nebulize the working calibration standard into the

plasma. The operator must sign and date the first page of standardization.

11.5.2. After the first CCB and before the ICS standards a CRA (MRL / LLICV / LLCCV) standard

is analyzed. Method 6020 requires the detection to be > the MDL but < 2x the MRL.

For 6020A, the criteria are 70-130% recovery. For DoD projects, the CRA criteria are

80-120%.

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Note: For 6020A the LLCCV must also be analyzed at the end on the analytical run

sequence.

11.5.3. Perform the analysis in the order listed below. A daily run log of all samples analyzed

is maintained.

Initial Calibration Verification (ICV)

Continuing Calibration Verification (CCV)

Initial Calibration Blank (ICB)

Continuing Calibration Blank (CCB)

CRA (MRL / LLICV / LLCCV)

ICSA

ICSAB

Analyze 10 Samples

CCV

CCB

Analyze 10 Samples

CCV

CCB

Repeat sequence as required to complete analytical run, analyzing CCVs/CCBs

every 10 analyses and at the end of the run.



The accuracy and precision of the procedure must be validated before analysis of samples

begins, or whenever significant changes to the procedures have been made. To do this, four

LCS aliquots are prepared and analyzed. The average percent recovery of for each analyte

must be 85-115% (for water, and within the LCS limits for soils) and the RSD <20%.

12.2. Method Detection Limits

12.2.1. A method detection limit (MDL) study must be undertaken before analysis of samples

can begin. To establish detection limits that are precise and accurate, the analyst must

perform the following procedure. Spike a minimum of seven blank matrices at a level

near or below the MRL. Follow the procedures starting in Section 11 to analyze the

samples. Refer to CE-QA011, Performing Method Detection Limit Studies and

Establishing Limits of Detection and Quantification details of performing the MDL

study.

12.2.2. Calculate the average concentration found (x) and the standard deviation of the

concentrations for each analyte. Calculate the MDL for each analyte using the correct

T value for the number of replicates. MDL’s must be verified annually or whenever

there is a significant change in the background or instrument response.

12.3. For method 6020A, an LLQC sample (a CRA that is carried through the digestion) must be

analyzed to verify accuracy at the MRL. The recovery must be 70-130%.

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12.4. Instrument Detection Limits (IDLs) and linear ranges studies are performed quarterly. These

will be calculated and made available to the ICP-MS operator. Linear range studies determine

the Linear Dynamic Range (LDR) of the each instrument by analysis of a high concentration

standard with results with ± 10% of the expected value. For non-DoD projects samples may be

quantified between the MRL and 90% of the LDR without flagging. The Linear Calibration

Range (LCR) is established by the highest calibration standard.

IDLs must be < LOD for DOD projects. DoD project samples with concentrations

above the calibration standard must be diluted to bring results within the quantitation

range. The LOQ and cal standard establish the quantitation range. The lab may report a

sample result above quantitation range if the lab runs and passes a CCV that is > sample

result.

12.5. The Initial Calibration Verification (ICV) standard is analyzed immediately after calibration. The

results of the ICV must agree within ±10% of the expected value. If the control limits are

exceeded, the problem will be identified and the instrument recalibrated.

12.6. A Continuing Calibration Verification (CCV) and Continuing Calibration Blank (CCB) are

analyzed after calibration then every 10 samples thereafter with a final CCV/CCB closing the

final samples of the analytical run.

12.6.1. The results of the CCV must agree within ±10% of the expected value.

12.6.2. The CCB measured values must be less than the MRL / LOQ for each element for

standard applications. Other project-specific criteria may apply (for DoD QSM projects

CCB can have no analytes > the LOD).

12.6.3. If the control limits are exceeded, the problem will be identified and corrective action

taken. The instrument recalibrated. The previous 10 samples must be reanalyzed.

12.7. The ICSA and ICSAB solutions are analyzed after calibration and before any field samples. The

solutions are then reanalyzed every 12 hours. Results of the ICSA are used by the analyst to

identify the impact of potential interferences on the quality of the data. Based on these results

appropriate action should be taken when interferences are suspected in an field sample

including, but not limited to, selecting and alternative isotope for quantification, manual

correction of the data, elevating the MRL, selection of an alternative method (e.g. optical ICP,

GFAA) or flagging the result as estimated when no other action is possible. Results for the

spiked analytes in the ICSAB solution must agree with ± 20% of the expected value.

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Concentrations (mg/L) Concentrations (mg/L)

Al 20.0 20.0

Ca 60.0 60.0

Fe 50.0 50.0

Mg 20.0 20.0

Na 50.0 50.0

P 20.0 20.0

K 20.0 20.0

S 20.0 20.0

C 40.0 40.0

Cl 424 424

Mo 0.05 0.05

Ti 0.40 0.40

As 0.0 0.025

Cd 0.0 0.025

Cr 0.0 0.050

Co 0.0 0.050

Cu 0.0 0.050

Mn 0.0 0.050

Ni 0.0 0.050

Se 0.0 0.025

Ag 0.0 0.0125

V 0.0 0.050

Zn 0.0 0.025

The concentration of interfering elements in the ICSA and ICSAB solutions are spiked at

levels 5 times lower than recommended in Table 1 of Method 6020A. Running the full

strength solutions as described in 6020A introduces too much material approximately 0.35 %

dissolved solids into the ICP-MS system when trying to conduct low level analysis. Since the

ICP-MS instrumentation is able to handle a maximum of 0.2% solids, the 6020A ICSA solution

is higher in interfering components than any sample that would run through the instrument.

However, the ICS solutions will be analyzed at levels that will provide approximately 0.1%

dissolved solids.

12.8. Internal standards are used to correct for physical interferences. Masses used as internal

standards include; 71

Ga, 115

In, 6

Li, 175

Lu, 103

Rh 45

Sc, and 89

Y. These internal standards are used in

combination to cover the appropriate mass ranges. Internal standard correction is applied to

the analytical isotopes via interpolation of the responses from nearest internal standard

isotopes (Thermo instruments) or direct correlation of analyte to IS (NexION). This function is

performed in real-time by the instruments operating system. Internal standards must be run

within 50 AMU of the masses that are analyzed. Internal standard recoveries must fall

between 30% and 125% when running method 6020, or 70-125% when running method

6020A Revision 1. If not, then the sample must be reanalyzed after a fivefold or greater

dilution has been performed.

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12.9. A method blank is digested and analyzed with every batch of 20 (or fewer) samples to

demonstrate that there are no method interferences. If the method blank shows any hits

above the MRL for standard applications, or >½ the MRL for DoD projects or > 1/10 the sample

result, corrective action must be taken. The MB can only be rerun once. Corrective action

includes recalculation, reanalysis, system cleaning, or re-extraction and reanalysis.

12.10. Laboratory Control Samples are analyzed at a frequency of 5% or one per batch, whichever is

greater. Refer to the current ALS-Kelso DQO spreadsheets for the LCS limits. For method

6020A, the LCS recovery limits are 80-120%. If statistical in-house limits are used, they must

fall within the 80-120% range. Project, QAPP, or client-specific control limits may supersede

the limits listed, but laboratory limits should be consistent with specified limits in order to

establish that the specified limits can be achieved. If the control limits are exceeded, the

associated batch of samples will be re-digested and reanalyzed.

12.11. A digested duplicate and matrix spike are analyzed at a frequency of 5% or one per batch,

whichever is greater. Refer to the current ALS-Kelso DQO spreadsheets for the matrix spike

limits. The matrix spike recovery and relative percent difference will be calculated while

analysis is in progress. Project, QAPP, or client-specific control limits may supersede the limits

listed. If the control limits are exceeded, the samples will be re-digested and reanalyzed,

unless matrix interference or sample non-homogeneity is established as cause. In these

instances, the data and the report will be flagged accordingly.

12.12. A Matrix Spike sample is digested one per batch, or per 20 samples (i.e. 5%). Default spike

concentrations are listed in the sample digestion SOPs. Spike concentrations may be adjusted

to meet project requirements. The matrix spike recovery will be calculated while the job is in

progress. Where specified by project requirements, a matrix spike duplicate may be required.

Matrix spike recovery criteria are derived from lab data. For method 6020A, the recovery limits

are 75-125%. If statistical in-house limits are used, they must fall within the 75-125% range. In

some cases, project-specific QC limits may be required. Unless specified otherwise, for DoD

QSM projects the project LCS criteria will be used for evaluation of matrix spikes. If an analyte

recovery is outside acceptance limits proceed with the additional quality control tests

described in sections 12.13 and 12.14. Based on results of these tests, the physical nature of

the sample (e.g. homogeneity), and any specific project requirements, a determination can

then be made as to appropriate corrective action (e.g. re-digestion, reporting with a qualifier,

alternative methodologies, etc.). If the analyte concentration is >4x the spike level the spike

control limit is no longer applicable and no action is required. For specifics on the preparation

and composition of matrix spike solutions refer to the appropriate digestion SOP.

For DOD projects a MS/MSD is required with every extraction batch. The %RSD should

be < 20%.

12.13. Post Digestion Spike Test: When analysis is conducted via 6020 a post digestion spike must

be performed for each matrix and each batch of sample. The prepared sample or its dilution is

spiked for each element of interest at a concentration sufficiently high to be observed.

Typically 20 µL of 10,000 ppb intermediate stock is added to a 10 mL aliquot of sample. If

analyte concentrations are elevated in the sample, spiking at a higher concentration may be

required. The post spike should be recovered to within 75-125% of the known value or within

the laboratory derived acceptance criteria. When analysis is conducted via 6020A, the post

digestion spike test is performed whenever matrix spike or replicate criteria are exceeded. An

analyte spike is added to a portion of a prepared sample, or its dilution, and should be

recovered to within 80% to 120% of the known value. If this spike fails, then the dilution test

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(Sec. 12.14) should be run on this sample. If both the matrix spike and the post digestion spike

fail, then matrix effects are confirmed.

12.14. Dilution Test: When analysis is conducted via 6020, a serial dilution test must be performed

for each matrix and each batch of sample. For sample concentrations that are sufficiently high

(minimally, a factor of greater than 100 times the MDL), the analysis of a fivefold (1+4) dilution

must agree within ± 10% of the original determination. When analysis is conducted via 6020A,

the dilution test is performed whenever matrix spike or replicate criteria and post digestion

spike criteria are exceeded. If the dilution test fails then a chemical or physical effect should be

suspected. Corrective action can include additional dilution of the sample, the use of alternate

methodologies, etc. or the data can be flagged and reported. The exact course of action will be

dependent on the nature of the samples and project requirements and should be discussed

with the project manager.

12.15. Instrument blanks should be evaluated for potential carryover and rinse times need to bring

the analyte signal to within the CCB criteria discussed above in section 12.6.2. Results from

instrument blanks run after standards or control samples should be used to establish levels at

which carryover in samples may occur. Samples exhibiting similar effects of carryover should

be reanalyzed.

12.16. Refer to the Quality Control section of EPA Methods 6020 and 6020A for additional

information describing required QA/QC. Note that the nomenclature of certain QC samples in

the method differs from that of the CLP SOW, but the function of those samples is equivalent

in both cases.

13. DATA REDUCTION AND REPORTING

13.1. Calculations

Calculate sample results using the data system printouts and digestion information. the

digestion and dilution information is entered into the data system. The data system then uses

the calculations below to generate a sample result.

Aqueous samples are reported in µg/L:


Solid samples are reported in mg/Kg:

1Kg

1000g x

1000ml

1L x

1000ug

1mg x

(g) wt.Sample

(ml) Vol. Digestion x Factor Dilution Digestion Post x C = (Sample) mg/Kg *

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NOTE: If results are to be reported on a dry weight basis, determine the dry weight of a

separate aliquot of the sample, using the SOP for Total Solids.

13.2. Common isobaric interferences are corrected using equations equivalent to those listed in EPA

Methods 6020, 6020A, and 200.8. Monitoring of multiple isotopes for a single element

provides a mechanism for identifying isobaric interferences. Refer to the Interferences section

of EPA methods for additional descriptions of possible interferences and the mechanisms

required for adequately compensating for their effects.

13.3. Data Review and Reporting

13.3.1. The ICP-MS operator reviews the MS data and signs and dates the Data Review Form.

A qualified senior staff spectroscopist performs a secondary review of the data and the

Data Review Form is signed and dated. The data is then delivered to the report

generation area where it is filed in the service request file. Once all of the data for the

service request is complete, a CAR is generated.

13.3.2. The data is saved on the local hard drive and is also copied to the appropriate directory

on the network. The data directories are located at r:\icp\wip\data. The data is kept

on the local directory for 1 month. The network files are periodically backed up on

disc or network tape.

13.3.3. For “non-production” work (such as method development or research/development

studies) the analyses are performed under the direction of a senior spectroscopist. All

associated data is scrutinized by the senior spectroscopist. Original raw data and

associated records are archived in the analytical project file.

13.3.4. The final review and approval of all data is performed by qualified spectroscopists.


14.1. Refer to the SOP for Nonconformity and Corrective Action (CE-QA008) for procedures for













acceptable levels

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error



to the reference method for additional available method performance data.

15.2. The method detection limit (MDL), limit of detection (LOD) and limit of quantitation (LOQ) are

established using procedures described in CE-QA011, Performing Method Detection Limit

Studies and Establishing Limits of Detection and Quantification. Method Reporting Limits are

established for this method based on MDL studies and as specified in the ALS, Kelso Quality

Assurance Manual.











All acid waste must be neutralized to a pH of 5-9 prior to disposal down the drain. The



17. TRAINING

17.1. Refer to the SOP ADM-TRAIN, ALS-Kelso Training Procedure for standard procedures.

17.2. A minimum of two senior level spectroscopists are to be maintained on staff at all times.

Senior spectroscopists are defined as individuals with a minimum of ten years combined

education and experience in, or related to atomic spectroscopy. Of those ten years, a

minimum of two years of ICP-MS experience is required.

17.3. All technical staff is encouraged to attend one technical seminar per year. In addition to the

technical seminars, senior spectroscopists are required to complete a one week training

session offered by the instrument manufacturer.

17.4. On-the-job-training occurs daily with the senior spectroscopists providing direction to new

operators. The physical operation of the equipment is relatively simple. The data reduction

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and troubleshooting requires extensive experience that can only be gained by hands-on

operation of the instrument and assisted evaluation of raw data.





17.5.2. The next training step is to assist in the procedure under the guidance of an

experienced analyst. During this period, the analyst is expected to transition from a

role of assisting, to performing the procedure with minimal oversight from an


17.5.3. Perform initial precision and recovery (IPR) study as described above for water or soil

samples. Summaries of the IPR are reviewed and signed by the supervisor. Copies may

be forwarded to the employee’s training file. For applicable tests, IPR studies should

be performed in order to be equivalent to NELAC’s Initial Demonstration of Capability.

17.6. Training and proficiency is documented in accordance with the SOP ADM-TRAIN.


18.1. There are no known modifications in this laboratory standard operating procedure from the

reference method.

19. REFERENCES

19.1. USEPA, Test Methods for Evaluating Solid Waste, SW-846, 3rd Edition, Update III Method 6020,

Revision 0, September 1994.

19.2. USEPA, Test Methods for Evaluating Solid Waste, SW-846, Update IV, Method 6020A, Revision

1, February 2007.

19.3. Agilent and Thermo Elemental Instrument Manuals


20.1. Reformatted SOP to current ALS format.

20.2. Minor changes (correct typos and errors, etc.) throughout SOP.

20.3. Section 1 – revised to eliminate redundant language.

20.4. Section 7.2.7.2 – updated to replace Excell with Agilent

20.5. Section 7.3 – revised to list specific internal standards and concentrations.

20.6. Section 8.1 – updated instrument information.

20.7. Section 11.4.2.3 – revised to correct peak height %.

20.8. Sections 12.10 and 12.12 – revised to refer to DQO tables for QC limits

20.9. Section 16 – revised to include default language.

20.10. Section 17 – revised to include default language and be consistent with 200.8 SOP.

20.11. Table 1 – updated.

20.12. Attachments updated.

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6020A EPA 3050B Aluminum Soil 0.6 2

6020A EPA 3050B Antimony Soil 0.02 0.05

6020A EPA 3050B Arsenic Soil 0.2 0.5

6020A EPA 3050B Barium Soil 0.02 0.05

6020A EPA 3050B Beryllium Soil 0.005 0.02

6020A EPA 3050B Bismuth Soil 0.02 0.05

6020A EPA 3050B Boron Soil 0.05 0.5

6020A EPA 3050B Cadmium Soil 0.009 0.02

6020A EPA 3050B Chromium Soil 0.07 0.2

6020A EPA 3050B Cobalt Soil 0.009 0.02

6020A EPA 3050B Copper Soil 0.04 0.1

6020A EPA 3050B Lead Soil 0.02 0.05

6020A EPA 3050B Manganese Soil 0.02 0.05

6020A EPA 3050B Molybdenum Soil 0.02 0.05

6020A EPA 3050B Nickel Soil 0.04 0.2

6020A EPA 3050B Selenium Soil 0.2 1

6020A EPA 3050B Silver Soil 0.005 0.02

6020A EPA 3050B Thallium Soil 0.002 0.02

6020A EPA 3050B Tin Soil 0.02 0.1

6020A EPA 3050B Uranium Soil 0.003 0.02

6020A EPA 3050B Vanadium Soil 0.08 0.2

6020A EPA 3050B Zinc Soil 0.2 0.5

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6020A MET-DIG (CLP) Aluminum Water 0.2 2

6020A MET-DIG (CLP) Antimony Water 0.01 0.05

6020A MET-DIG (CLP) Arsenic Water 0.05 0.5

6020A MET-DIG (CLP) Barium Water 0.006 0.05

6020A MET-DIG (CLP) Beryllium Water 0.008 0.02

6020A MET-DIG (CLP) Bismuth Water 0.005 0.05

6020A MET-DIG (CLP) Boron Water 0.07 0.5

6020A MET-DIG (CLP) Cadmium Water 0.005 0.02

6020A MET-DIG (CLP) Chromium Water 0.02 0.2

6020A MET-DIG (CLP) Cobalt Water 0.006 0.02

6020A MET-DIG (CLP) Copper Water 0.03 0.1

6020A MET-DIG (CLP) Iron Water 0.3 1

6020A MET-DIG (CLP) Lead Water 0.004 0.02

6020A MET-DIG (CLP) Manganese Water 0.006 0.05

6020A MET-DIG (CLP) Molybdenum Water 0.008 0.05

6020A MET-DIG (CLP) Nickel Water 0.04 0.2

6020A MET-DIG (CLP) Selenium Water 0.4 1

6020A MET-DIG (CLP) Silver Water 0.005 0.02

6020A MET-DIG (CLP) Thallium Water 0.005 0.02

6020A MET-DIG (CLP) Tin Water 0.01 0.05

6020A MET-DIG (CLP) Uranium Water 0.003 0.02

6020A MET-DIG (CLP) Vanadium Water 0.05 0.2

6020A MET-DIG (CLP) Zinc Water 0.09 0.5

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6020A PSEP TISSUE Aluminum Tissue 0.2 2

6020A PSEP TISSUE Antimony Tissue 0.002 0.05

6020A PSEP TISSUE Arsenic Tissue 0.02 0.5

6020A PSEP TISSUE Barium Tissue 0.005 0.05

6020A PSEP TISSUE Beryllium Tissue 0.003 0.02

6020A PSEP TISSUE Bismuth Tissue 0.003 0.05

6020A PSEP TISSUE Boron Tissue 0.2 2

6020A PSEP TISSUE Cadmium Tissue 0.002 0.02

6020A PSEP TISSUE Chromium Tissue 0.02 0.2

6020A PSEP TISSUE Cobalt Tissue 0.003 0.02

6020A PSEP TISSUE Copper Tissue 0.02 0.1

6020A PSEP TISSUE Iron Tissue 0.2 1

6020A PSEP TISSUE Lead Tissue 0.0005 0.02

6020A PSEP TISSUE Manganese Tissue 0.008 0.05

6020A PSEP TISSUE Molybdenum Tissue 0.008 0.05

6020A PSEP TISSUE Nickel Tissue 0.02 0.2

6020A PSEP TISSUE Selenium Tissue 0.2 1

6020A PSEP TISSUE Silver Tissue 0.006 0.02

6020A PSEP TISSUE Thallium Tissue 0.0009 0.02

6020A PSEP TISSUE Tin Tissue 0.003 0.05

6020A PSEP TISSUE Uranium Tissue 0.0008 0.02

6020A PSEP TISSUE Vanadium Tissue 0.007 0.2

6020A PSEP TISSUE Zinc Tissue 0.06 0.5

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DOCUMENT TITLE: DETERMINATION OF METALS AND TRACE ELEMENTS

BY INDUCTIVELY COUPLED PLASMA ATOMIC

EMISSION SPECTROMETRY (ICP)

REFERENCED METHOD: EPA 200.7/6010C

SOP ID: MET-ICP

REVISION NUMBER: 25


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TABLE OF CONTENTS

1.SCOPE AND APPLICATION ......................................................................................................................... 3 2.METHOD SUMMARY ................................................................................................................................... 3 3.DEFINITIONS ................................................................................................................................................ 3 4.INTERFERENCES .......................................................................................................................................... 5 5.SAFETY ......................................................................................................................................................... 5 6.SAMPLE COLLECTION, CONTAINERS, PRESERVATION AND STORAGE ............................................... 6 7.STANDARDS, REAGENTS, AND CONSUMABLE MATERIALS................................................................... 6 8.APPARATUS AND EQUIPMENT .................................................................................................................. 8 9.PREVENTIVE MAINTENANCE ..................................................................................................................... 8 10.RESPONSIBILITIES ...................................................................................................................................... 8 11.PROCEDURE .............................................................................................................................................. 8 12.QA/QC REQUIREMENTS........................................................................................................................... 11 13.DATA REDUCTION, REVIEW, AND REPORTING .................................................................................... 14 14.CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA ......................... 15 15.METHOD PERFORMANCE ........................................................................................................................ 15 16.POLLUTION PREVENTION AND WASTE MANAGEMENT ...................................................................... 16 17.TRAINING .................................................................................................................................................. 16 18.METHOD MODIFICATIONS ...................................................................................................................... 16 19.REFERENCES .............................................................................................................................................. 16 20.CHANGES SINCE THE LAST REVISION .................................................................................................... 17

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DETERMINATION OF METALS AND TRACE ELEMENTS BY INDUCTIVELY COUPLED PLASMA

ATOMIC EMISSION SPECTROMETRY (ICP)


1.1. This procedure describes the steps taken for the analysis of soil, sludge surface water and

drinking water digestates using EPA methods 6010C, 200.7, and CLP ILM04.0 for a variety of

elements. The digested samples and QC standards are all diluted in a similar acid matrix. A

procedure is also given for calculation of hardness by Standard Methods 2340B.

1.2. The Method Reporting Limits (MRLs) for common elements are listed in Table 1. Equivalent

nomenclature for MRL includes Estimated Quantitation Limit (EQL). Therefore, MRL=EQL. The

reported MRL may be adjusted if required for specific project requirements, however, the

capability of achieving other reported MRLs must be demonstrated. The Method Detection

Limits (MDLs) that have been achieved are listed in Table 1. The MDL and MRL may change as

annual studies are performed.

1.3. In cases where there is a project-specific quality assurance plan (QAPP), the project manager

identifies and communicates the QAPP-specific requirements to the laboratory. In general,

project specific QAPP’s supersede method specified requirements. An example of this are

projects falling under DoD ELAP or project which require older versions of EPA methods (i.e.

6010B). QC requirements defined in the SOP Department of Defense Projects – Laboratory

Practices and Project Management (ADM-DOD) may supersede the requirements defined in

this SOP.

2. METHOD SUMMARY

2.1. A representative aliquot of sample is prepared as described in the applicable digestion SOP.

The digestate is analyzed for the elements of interest using ICP spectrometry. The instrument

measures characteristic emission spectra by optical spectrometry. The intensity of emission

lines are monitored.

2.2. Final results are calculated using the digestion information and the results from the ICP

analysis. Data is reported using standard ALS procedures and formats, or following project

specific reporting specifications.

2.3. Deviations from the reference method(s): This SOP contains no deviations from the reference

methods.

3. DEFINITIONS




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3.1.1. Preparation Batch - A preparation batch is composed of one to twenty field samples, all

of the same matrix, and with a maximum time between the start of processing of the

first and last samples in the batch to be 24 hours.

3.1.2. Analysis Batch - Samples are analyzed in a set referred to as an analysis sequence. The

sequence begins with instrument calibration (initial or continuing verification) followed

by sample extracts interspersed with calibration standards (CCBs, CCVs, etc.) The

sequence ends when the set of samples has been injected or when qualitative and/or

quantitative QC criteria indicate an out-of-control situation.

3.2.









3.3.1. Aqueous - Any groundwater sample, surface water sample, effluent sample, and TCLP

or other extract. Specifically excluded are samples of the drinking water matrix and the

saline/estuarine water matrix.

3.3.2. Drinking water - Any aqueous sample that has been designated a potable or potential

potable water source.

3.3.3. Saline/Estuarine water - Any aqueous sample from an ocean or estuary or other salt-

water source.

3.3.4. Non-aqueous Liquid - Any organic liquid with <15% settleable solids.

3.3.5. Animal tissue - Any tissue sample of an animal, invertebrate, marine organism, or other

origin; such as fish tissue/organs, shellfish, worms, or animal material.


settleable solids.

3.3.7. Chemical waste - Any sample of a product or by-product of an industrial process that

results in a matrix not described in one of the matrices in Sections 3.3.1 through 3.3.6.

These can be such matrices as non-aqueous liquids, solvents, oil, etc.

3.3.8. Miscellaneous matrices – Samples of any composition not listed in 3.3.1 – 3.3.7. These

can be such matrices as plant material, paper/paperboard, wood, autofluff, mechanical

parts, filters, wipes, etc. Such samples shall be batched/grouped according to their

specific matrix.

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3.4. Matrix Spike/Duplicate Matrix Spike (MS/DMS) Analysis - In the matrix spike analysis,

predetermined quantities of target analytes are added to a sample matrix prior to sample

preparation and analysis. The purpose of the matrix spike is to evaluate the effects of the

sample matrix on the method used for the analysis. Duplicate samples are spiked, and

analyzed as a MS/DMS pair. Percent recoveries are calculated for each of the analytes

detected. The relative percent difference (RPD) between the duplicate spikes (or samples) is

calculated and used to assess analytical precision. The concentration of the spike should be at

the midpoint of the calibration range or at levels specified by a project analysis plan.

3.5. Laboratory Duplicates (DUP) – Duplicates are additional replicates of samples that are

subjected to the same preparation and analytical scheme as the original sample. The relative

percent difference (RPD) between the sample and its duplicate is calculated and used to assess

analytical precision.

3.6. Method Blank (MB) - The method blank is an artificial sample composed of analyte-free water



3.7. Laboratory Control Samples (LCS) – The LCS is an aliquot of analyte free water or analyte free

solid to which known amounts target analytes are added. The LCS is prepared and analyzed in

exactly the same manner as the samples. The percent recovery is compared to established

limits and assists in determining whether the batch is in control.

3.8. Laboratory fortified Blank (LFB) - A laboratory blank that has been fortified with target analyte

at the method reporting limit and used to determine if the laboratory can detect contaminants

at the method reporting limit.

3.9. Independent Verification Standard (ICV) - A mid-level standard injected into the instrument

after the calibration curve and prepared from a different source than the initial calibration

standards. This is used to verify the validity of the initial calibration standards

3.10. Continuing Calibration Verification Standard (CCV) - A standard analyzed at specified intervals

and used to verify the ongoing validity of the instrument calibration.

3.11. Instrument Blank (CCB) - The instrument blank (also called continuing calibration blank) is a

volume of blank reagent of composition identical to the digestates. The purpose of the CCB is

to determine the levels of contamination associated with the instrumental analysis.

4. INTERFERENCES

4.1. Interferences from contaminated reagents must be eliminated. The purity of acids must be

established by the laboratory as being high enough to eliminate the introduction of

contamination above the MRL (or above ½ the RL for DoD work).

4.2. Background emission and stray light can be compensated by background correction.

4.3. Spectral overlaps resulting in interelement contributions can be corrected for by using

interelement correction factors. Interelement correction factors are established for each

instrument and are maintained by the analyst at the workstation.

5. SAFETY

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5.2. Hydrochloric, Nitric and Hydrofluoric Acids are used in this method. These acids are extremely

corrosive and care must be taken while handling them. A face shield should be used while

pouring acids. Safety glasses, lab coat and gloves should be worn while working with the

solutions.

5.3. High Voltage - The power unit supplies high voltage to the RF generator which is used to form

the plasma. The unit should never be opened. Exposure to high voltage can cause injury or

death.

5.4. UV Light -The plasma when lit is a very intense light, and must not be viewed with the naked

eye. Protective lenses are in place on the instrument. Glasses with special protective lenses

are available.


6.1. Samples are prepared using methods 3005A, 3010A, 3050, or CLPILM04.0 (ALS SOPs MET-

3005A, MET-3010A, MET-3050, and MET-DIG). Samples are received in the ICP lab as

completed digestates. Samples are stored in 50 mL plastic centrifuge tubes, 100 mL digestion

vessels or in 100 mL volumetric flasks.

6.2. Water samples analyzed by EPA method 200.7 are preserved after arrival at the laboratory.

These samples are held for a minimum of 24 hours and the pH verified to be <2 prior to

digestion.

6.3. Soil samples are diluted prior to instrumental analysis by a factor of 2. This allows the method

to meet the required 1 g of sample to 200 mL dilution during digestion.

6.4. Following analysis, digestates are stored until two weeks after all results have been reviewed

and then brought to 3< pH<10 and disposed of through the sewer system.


7.1. Standards Preparation

7.1.1. Stock standard solutions may be purchased from a number of vendors. All reference

standards, where possible, must be traceable to SI units or NIST certified reference

materials. The preparation for all laboratory prepared reagents and solutions must be

documented in a laboratory logbook. Refer to the SOP Reagent/Standards Login and

Tracking (ADM-RTL) for the complete procedure and documentation requirements.

Manufacturer’s expiration dates are used to determine the viability of standards.

7.1.2. Calibration Standards

Calibration standards are prepared from commercially purchased single element 1000

ppm or 10,000 ppm stock standards as well as pre-mixed multi element stock

standards. All standards are aliquoted using Class A volumetric pipettes, or calibrated

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fixed and adjustable volume autopipetters. All dilutions are made in Class A

volumetric glassware.

The standard mixes for each ICP system vary based on the requirements of each

instrument. The composition of the ICAP 6500 standards are outlined in Table 2.

7.1.3. Continuing Calibration Verification (CCV) Standards

CCV standards are analyzed at the midpoint of the calibration. These standards are

produced by making a two-fold dilution of each calibration standard. The CCV

standards are then run in sequence during the analytical run.

7.1.4. Initial Calibration Verification (ICV) Standards

The ICV working standards are produced by direct dilution of two certified mixed stock

solutions (QCP-CICV1 and QCP-CICV3 purchased from Inorganic Ventures or another

qualified vendor and various single element stock solutions from sources different

than the calibration standards. The composition of these standards is outlined in Table

3.

7.1.5. Interference Check Solutions (ICSA & ICSAB)

The ICSA and ICSAB working standards are produced by direct dilution of certified

mixed stock solutions (CLPP-ICS-A and CLPP-ICS-B or equivalent.) Antimony is also

added to the ICSAB solution from a 1000 ppm single element stock standard. The

composition of these standards is outlined in Table 4.

7.1.6. CRI/Low Level Calibration Verification

The CRI, Low Level Initial Calibration Verification (LLICV), and Low Level Continuing

Calibration Verification (LLCCV) are produced by diluting 1000 or 10000ppm single

stock standards into a 100X intermediate standard and then diluted 1/100 to obtain

the MRL level. Note: The level used is that of the normal MRL used for both

instruments.

7.1.7. The solutions and materials used for the LCS and matrix spikes are described in the

applicable digestion SOP.

7.1.8. Standard Log

The analyte, source, initial volume, final volume, final concentration and expiration

date are recorded in a standard logbook kept in the ICP lab. The operator who

prepares the standard must date and initial the entry in the standards logbook. The

operator also places his initials and the date prepared on the standard container. In

addition to working standards used in calibration, all other standards used in the

analytical run such as ICVs, MRL standards, and other project or client specific

standards shall be documented in the standard logbook.

7.2. High Purity Argon.

7.3. Capillary, rinse and peristaltic pump tubing.

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7.4. 17 x 100mm polypropylene test tubes.


8.1. Inductively Coupled Plasma Atomic Emission Spectrometer

8.1.1. Thermo Scientific ICAP 6500 (AES-03).

8.1.2. Thermo Scientific ICAP 6500 (AES-04).

8.2. Concentric nebulizers.

8.3. Microflow nebulizer for ICAP 6500.

8.4. Torches and injector tips for each ICP.

8.5. Cyclonic spray chambers for each instrument.

8.6. Water coolers for each ICP.

8.7. Argon Humidifiers for the ICAP 6500.

8.8. ESI SC4 DX Autosampler with Fast System for ICAP 6500.

8.9. Peristaltic Pumps for each Spectrometer.

8.10. RF Generators for each ICP (internal on the IRIS and ICAP 6500).


9.1. All maintenance activities are recorded in a maintenance logbook kept for each instrument.

Pertinent information (serial numbers, instrument I.D., etc.) must be in the logbook. This

includes the routine maintenance described in section 9. The entry in the log must include:

date of event, the initials of who performed the work, and a reference to analytical control.

9.2. Torch, nebulizer, and spray chambers are cleaned as required. All instrument filters are

vacuumed monthly. Dirty ICP torches and mixing chambers are soaked in aqua regia

overnight, rinsed and placed in a clean dry area. The conical nebulizer is back flushed with

acid or DI water as needed. The microflow nebulizer is not back flushed. Use the obstruction

removal kit.









Training and proficiency is documented in accordance with the SOP ADM-TRANDOC.

11. PROCEDURE

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11.1. Operating Parameters

11.1.1. For each Thermo Scientific ICAP 6500, the operating parameters are defined in the

Method file. Default operating parameters are given in Tools/Options/New

Method Parameters. However, each unique set of operating parameters is saved

as a new file and the analyst must select and use the correct Method file for the

application. Refer to the method files on the workstation for a listing of

parameters for each file. The interelement correction factors to be used are

established for the ICAP 6500 and are saved on the workstation also. Since these

parameters change with method and correction factor updates, and due to the

large amount of hardcopy printout for listing these parameters, it is not practical

to include the parameters in this SOP.

11.2. Calibration/Standardization

11.2.1. ICAP 6500

11.2.1.1.Plasma is ignited and instrument is allowed to warm up for at least 30

minutes.

11.2.1.2.An internal standard is used for routine analyses on this instrument.

Yttrium and Indium are used as internal standards. The internal standard

solution is introduced into the analyzed solutions (standards, blanks, QC,

samples, etc.) at 0.8 ug/mL for Y, and 1.6 ug/mL for In.

11.2.1.3.Run a peak check standard and adjust peaks as needed.

11.2.1.4.Standardize by running a Blank and a High Standard for each element in

the analytical method. Analyst will initial and date the first page of the

standardization.

11.2.2. Standardization is completed by analyzing an ICV for each analyte to be

determined. For method 200.7 the result must be within ±5% of the true value.

For method 6010B/C the result must be within ±10% of the true value. If the ICV

fails when running method 6010C, either the calibration standards or the ICV

must be prepared fresh and the instrument re-standardized. If the ICV fails when

running methods 200.7 and 6010B only re-standardization is necessary.

11.2.3. Method 6010C also requires a LLICV be analyzed at the MRL level. The result

must be within ±30% of the true value. The LLICV need not be made up with stock

standards different than those of the calibration standards.

11.3. Analytical Run

11.3.1. Following standardization and ICV analysis, the remainder of the run is determined

by what analytical method is being performed. These are listed below.

11.3.1.1.CLP ILM04.0: ICB, CCV, CCB, CRI, ICSA, ICSAB, CCV, CCB, routine

samples. The CRI, ICSA, and ICSAB will be analyzed every 20 samples.

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They will be labeled with an F indicating Final. Each set will be numbered

in increasing order, i.e. ICSAF1, ICSAF2.

11.3.1.2.Methods 200.7 and 6010B/C: ICB, LLICV, CCV, CCB, CRI, ICSA, ICSAB,

routine samples.

11.3.2. Evaluate the initial QC using the following criteria:

11.3.2.1.For methods 200.7 and 6010B/C, the following criteria apply:

The ICB and CCB results are evaluated using method specified

requirements. The following guidelines should also be used to

determine acceptability:

For 200.7, the result should be less than 3 times the standard

deviation of the mean background signal.

For method 6010B, the result should be less than the Method

Detection Limit (MDL). In cases where the associated sample results

are being reported to the Method Reporting Limit (MRL) the result

may be greater than the MDL if the result does not adversely impact

data quality.

For method 6010C, the result should be less than the Lower Limit

of Quantitation (LOQ).

Where project specifications allow, the result may be over the MDL

if the result does not adversely impact data quality.

The CCV immediately following standardization must verify within

± 10% of the true values with a relative standard deviation of <5%

from 2 replicate integrations for methods 6010B/C. For 200.7, the

first CCV must verify within ± 5% with a RSD of <3% from 4

replicates. Calculate %RSD as follows:

100% xAverage

StdDev = RSD

CCV

CCV

where: StdDevccv = Standard deviation of the replicate integrations

Averageccv = Average of the replicate CCV integrations

The LLICV or CRI is a low level standard with concentrations at the

RL. For DoD projects, the LLICV standard concentrations will be

equal to the project RLs. For method 6010C the CRI results should

be within 30% of the true value. For 200.7 and 6010B the LLICV/CRI

results should be greater than the MDL and less than 2X the MRL.

For method 6010C, the LLICV results should be ± 30% of the true

value.

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The ICSA is run to check the validity of the Interelement Correction

Factors (IECs).

DoD QSM requires this to be run at the beginning of each analytical

run.

The ICSAB must be within 20% of the expected value for the CLPP-

ICS-B elements and Sb.

11.3.2.2.The ICV, LLICV, ICB, CCV, CCB, CRI, and ICSAB must meet the criteria

listed. Reanalyze any elements that fail.

11.3.2.3.For CLP, refer to SOW ILM04.0 for acceptance criteria.

11.3.3. Continuing Calibration Verification

11.3.3.1.CCVs are analyzed after every 10 samples and at the end of the analytical

run. They must verify within ±10% of the expected value with a RSD of

<10%.

11.3.3.2.CCBs are analyzed after every 10 samples and at the end of the analytical

run. CCBs are evaluated as in section 11.3.2.1.

11.3.3.3.Method 6010C requires a LLCCV be analyzed at the end of each analysis

batch. The LLCCV is at the MRL level and must verify within ±30% of the

true value. Reanalyze any elements to be reported at low levels that are

bracketed by the LLCCV if the standard fails.

11.3.4. If the CCV or CCB solutions fail, reanalyze any elements to be reported.



The accuracy and precision of the procedure must be validated before analysis of samples

begins, or whenever significant changes to the procedures have been made. To do this, four

LCS aliquots are prepared and analyzed. The average percent recovery for each analyte must

meet LCS criteria and the RSD< 30%.

12.2. Method Detection Limits

12.2.1. A Method Detection Limit (MDL) study must be undertaken before analysis of samples

can begin. To establish detection limits that are precise and accurate, the analyst must

perform the following procedure. Spike a minimum of seven blank replicates at a level

near or below the MRL. Follow the procedures in Section 11 to analyze the samples.

Refer to the SOP CE-QA011, Performing Method Detection Limit Studies and

Establishing Limits of Detection and Quantification.

12.2.2. Calculate the average concentration found (x) and the standard deviation of the

concentrations for each analyte. Calculate the MDL for each analyte using the correct

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T value for the number of replicates. MDLs must be performed whenever there is a

significant change in the background or instrument response.

12.2.3. A Limit of Detection (LOD) check must be performed after establishing the MDL and at

least annually (quarterly if DoD) afterward. A blank is spiked with analytes at 2-4X the

MDL and carried through the preparation and analytical procedure. The LOD is verified

when the signal/noise ratio is > 3 for all analytes.

12.3. Limit of Quantitation Check(LOQ)/Lower Limit of Quantitation Check(LLQC)

For Method 6010C and drinking waters by method 200.7 a Lower Limit of Quantitation Check

(LOQ/LLOQ) sample must be analyzed after establishing the MRL and at least annually

(quarterly if DoD) afterward to demonstrate the desired detection capability. The LOQ/LLOQ

sample is spiked at 1-2X the MRL and must be carried through the entire preparation and

analytical procedure. Limits of quantitation are verified when all analytes are detected within

30% of their true value.

12.4. Linear Dynamic Range

The upper limit of the LDR must be established for each wavelength utilized. It must be

determined from a linear calibration prepared in the normal manner using the established

analytical operating procedure for the instrument. The LDR should be determined by analyzing

at least three succeeding higher standard concentrations of the analyte until the observed

analyte concentration is no more than 10% above or below the stated concentration of the

standard. Determined LDRs must be documented and kept on file. The LDR which may be used

for the analysis of samples should be judged by the analyst from the resulting data. Sample

analyte concentrations that are greater than 90% of the determined upper LDR limit must be

diluted and reanalyzed. The LDRs are verified semi-annually or whenever, in the judgment of

the analyst, a change in analytical performance caused by either a change in instrument

hardware or operating conditions would dictate they be redetermined.

12.5. Instrument Detection Limit

On a quarterly basis, the instrument detection limits for all analytes are determined as per

procedures outlined in ILM04.0 (Section E, paragraph 10, 12 resp.). IDLs are determined using

blanks and this data is kept on file.

12.6. Interelement Correction Factors

Semi-annually, instrument interferences are calculated as per ILM04.0 (Section E, paragraph

11) and Method 6010B/C. During the course of routine work, other interferences may be

found. They are verified by the operator during the analytical run and data is manually

corrected. Copies of this data are kept on file. Data can be manually corrected or

automatically corrected using iTEVA software.

12.7. Internal Standard

Internal standard values are tracked by the instrument software. Values should remain within

60-125% of the value found in the calibration blank. If a sample is found to have and internal

standard outside this value, the sample will be diluted to bring the internal standard into

range.

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12.8. Ongoing QC Samples required are described in the ALS-Kelso Quality Assurance Manual and in

the SOP for Sample Batches. Additional QC Samples may be required in project specific quality

assurance plans (QAPP). For example projects managed under the DoD ELAP must follow

requirements defined in the DoD Quality Systems Manual for Environmental Laboratories.

General QA requirements for DoD QSM are defined in the laboratory SOP, Department of

Defense Projects – Laboratory Practices and Project Management (ADM-DOD). General QC

Samples are:

12.8.1. Each sample preparation batch must have a method blank associated with it. The

method blank result should be < MRL. If the method blank is found to be

contaminated, it may be reported if the concentration in the associated samples is at

least 20 times the amount found in the method blank for methods 200.7 and 6010B,

otherwise redigest the batch. For Method 6010C, the method blank may be reported if

the concentration in the associated samples is at least 10 times the amount found in

the method blank.A contaminated method blank (MB) may also be reported if all of the

associated samples are non-detect (ND).

DoD QSM requires contamination in the MB be <1/2 the RL or < 1/10 any

sample amount.

12.8.2. A Laboratory Control Sample (LCS) is digested one per batch, or per 20 samples. For

soil samples, the recovery must fall within the ranges specified for the reference

material. For CLP, use the prescribed limits for the SOW in use. If the LCS fails the

acceptance criteria, redigest the batch of samples. For specifics on the preparation and

composition of LCS samples refer to the appropriate digestion SOP.

12.8.3. A Duplicate sample is digested one per batch, or per 20 samples (i.e. 5%) for 6010B/C

analysis, or per 10 samples (i.e. 10%) for 200.7 analyses. If the RPD is outside

acceptance limits, either redigest the sample batch or flag the data appropriately,

depending on the physical nature of the samples (e.g. non-homogenous).

12.8.4. A Laboratory fortified Blank (LFB) at the MRL is digested and analyzed with every batch

of drinking water samples (method 200.7). The default acceptance criteria of 50-150%

are to be used until sufficient data points are acquired to calculate in-house control

limits.

12.8.5. A Matrix Spike sample is digested one per batch, or per 20 samples (i.e. 5%) for

6010B/C analysis, or per 10 samples (i.e. 10%) for 200.7 analyses. Where specified by

project requirements, a matrix spike duplicate may be required. If the recovery is

outside acceptance limits, either redigest the sample batch or flag the data

appropriately, depending on the physical nature of the samples (e.g. non-

homogenous). If the sample concentration is >4x the spike level, no action is required

and data is flagged accordingly. For specifics on the preparation and composition of

matrix spike solutions refer to the appropriate digestion SOP.

12.8.6. Acceptance criteria

12.8.6.1.Current ALS control limits and acceptance criteria for ongoing QC analyses

are listed in the current ALS-Kelso DQO tables. Criteria are subject to change as

statistical data are generated. The default method criteria may be used if

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statistically generated criteria are broader or insufficient points are available

for accurate statistical limits.

12.8.6.2.For all QC analyses, project-specific or program-specific (e.g. DOD) acceptance

criteria may supersede ALS criteria. For analyses under the CLP SOW use the

prescribed limits for the SOW in use.

12.8.7. Matrix Interference

12.8.7.1.When an analyst suspects that there may be any matrix interferences present,

a post digestion spike may be performed. The recovery should be ± 20%.

12.8.7.2.If the post spike fails, a 1:5 serial dilution test shall be performed. The

dilution should be within ± 10% of the original result.

12.8.7.3. A 1:5 serial dilution shall be performed for all Tier III or IV deliverables.

DoD QSM recovery acceptance limits are 75-125%.

12.8.7.4.Post spikes for 6010C shall be performed for Tier III and Tier 1V.

12.9. Additional QC measures include control charting and compiling of QC data for generation of

control limits.

12.10. CLP analyses are performed as per the QA/QC guidelines in the most current CLP SOW.

13. DATA REDUCTION, REVIEW, AND REPORTING

13.1. Calculate sample results using the data system printouts and digestion information. The

digestion and dilution information is entered into the data system. The data system then uses

the calculations below to generate a sample result. The wavelengths used to quantify each

metal are summarized in Table 5 for the IRIS and Table 6 for the ICAP6500.

Aqueous samples are reported in ug/L:

mggFactor Dilution Digestion Post x Factor Dilution Digestion x C = (Sample) g/L * /1000

Solid samples are reported in mg/Kg:

1Kg

1000g x

1000ml

1L x

(g) wt.Sample

(ml) Vol. Digestion x Factor Dilution Digestion Post x C = (Sample) mg/Kg *

C*= Concentration of analyte as measured at the instrument in mg/L.

13.2. If total hardness is to be reported, use Calcium and Magnesium results to calculate as follows.

For reporting calcium hardness, use only the calcium portion of the equation.

LmgMgLmgCa = /LCaCOequivalentmgHardness /,118.4/,497.2, 3

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13.3. A daily run log of all samples analyzed is maintained. All CLP data should be printed and

stored after operator has checked for evenness of burns. A copy of this document will go with

each package of Tier III or higher data run that day.

13.4. Data Review and Reporting

13.4.1. It is the analyst’s responsibility to review analytical data to ensure that all quality

control requirements have been met for each analytical run. Results for QC analyses

are calculated and recorded as specified in section 12. The data is then placed in a

work order file until complete. When the work order is complete, a report is generated.

A final review is performed and the data is delivered to the project management

department.


14.1. Refer to the SOP for Nonconformance and Corrective Action (CE-QA008) for procedures for













acceptable levels






error



to the reference method for additional available method performance data.

15.2. The method detection limit (MDL) is established using the procedure described in the SOP CE-

QA011, Performing Method Detection Limit Studies and Establishing Limits of Detection and

Quantification. Method Reporting Limits are established for this method based on MDL

studies and as specified in the ALS Quality Assurance Manual.

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All acid waste must be neutralized to a pH of 3-10 prior to disposal down the drain. The



17. TRAINING





17.1.2. Assist in the procedure under the guidance of an experienced analyst for

approximately two weeks. During this period, the analyst is expected to transition

from a role of assisting, to performing the procedure with minimal oversight from an


17.1.3. Perform initial precision and recovery (IPR) study as described above for water samples.

Summaries of the IPR are reviewed and signed by the supervisor. Copies may be

forwarded to the employee’s training file. For applicable tests, IPR studies should be

performed in order to be equivalent to NELAP Initial Demonstration of Capability.

17.2. Training is documented following the ALS Kelso, Training Procedure (ADM-TRAIN) and the

Corporate Training Policy (CE-QA003).

NOTE: When the analyst training is documented by the supervisor on internal training

documentation forms, the supervisor is acknowledging that the analyst has read and

understands this SOP and that adequate training has been given to the analyst to competently

perform the analysis independently.


18.1. There are no known modifications in this laboratory standard operating procedure from the

reference method.

19. REFERENCES

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19.1. USEPA, Contract Laboratory Program, SOW #ILM04.0

19.2. Thermo Jarrell Ash ICAP61 Manual

19.3. USEPA, Test Methods for Evaluating Solid Waste, SW-846, 3rd Edition, Update III, Method

6010B, Revision 2, December 1996.

19.4. USEPA, Test Methods for Evaluating Solid Waste, SW-846, 3rd Edition, Update III, Method

6010C, Revision 3, February 2007.

19.5. USEPA, Methods for Determination of Metals in Environmental Samples, Supplement I,

EPA/600/R-94/111, Method 200.7, Revision 4.4, May 1994.

19.6. Hardness by Calculation, Method 2340B, Standard Methods for the Examination of Water and

Wastewater, 20th ed., 1998.


20.1. Updated to current ALS format.

20.2. Revised internal document references from CAS to ALS

20.3. Minor typographical and format corrections.

20.4. Section 3– updated several definitions to standard definitions for SOPs.

20.5. Section 7.1.4 – corrected standard composition to reflect current practice.

20.6. Section 9.2 – revised to reflect current practice.

20.7. Section 11.3.2.1 – LL ICV criteria revised to reflect current practice.

20.8. Section 12.2.3 – LOD spike level corrected.

20.9. Section 12.4 – revised to reflect current practice (LDR semi-annual).

20.10. Sections 12.8.2. – 12.8.5 revised to remove outdated/redundant QC criteria and added new

section 12.8.6.

20.11. Section 14 – updated to standard language.

20.12. Section 17 – updated to standard language.

20.13. Tables reference errors corrected and tables updated.

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METHOD PREP METHOD ANALYTE MATRIX MDL MRL

0.7 EPA 3050B Aluminum Soil 0.5 2

200.7 EPA 3050B Antimony Soil 2 4

200.7 EPA 3050B Arsenic Soil 2 4

200.7 EPA 3050B Barium Soil 0.3 0.8

200.7 EPA 3050B Beryllium Soil 0.08 0.2

200.7 EPA 3050B Bismuth Soil 3 8

200.7 EPA 3050B Boron Soil 0.7 4

200.7 EPA 3050B Cadmium Soil 0.09 0.2

200.7 EPA 3050B Calcium Soil 1 4

200.7 EPA 3050B Chromium Soil 0.3 0.8

200.7 EPA 3050B Cobalt Soil 0.2 0.4

200.7 EPA 3050B Copper Soil 0.4 0.8

200.7 EPA 3050B Iron Soil 2 4

200.7 EPA 3050B Lead Soil 0.7 2

200.7 EPA 3050B Lithium Soil 0.6 4

200.7 EPA 3050B Magnesium Soil 0.2 2

200.7 EPA 3050B Manganese Soil 0.04 0.2

200.7 EPA 3050B Molybdenum Soil 0.2 0.8

200.7 EPA 3050B Nickel Soil 0.2 0.8

200.7 EPA 3050B Phosphorus Soil 3 8

200.7 EPA 3050B Potassium Soil 10 40

200.7 EPA 3050B Selenium Soil 2 4

200.7 EPA 3050B Silver Soil 0.3 0.8

200.7 EPA 3050B Sodium Soil 5 40

200.7 EPA 3050B Strontium Soil 0.05 0.2

200.7 EPA 3050B Sulfur Soil 4 8

200.7 EPA 3050B Thallium Soil 0.8 2

200.7 EPA 3050B Tin Soil 0.6 4

200.7 EPA 3050B Titanium Soil 0.2 0.4

200.7 EPA 3050B Vanadium Soil 0.3 0.8

200.7 EPA 3050B Zinc Soil 0.2 1

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200.7 MET-DIG (CLP) Aluminum Water 4 10

200.7 MET-DIG (CLP) Antimony Water 6 20

200.7 MET-DIG (CLP) Arsenic Water 5 10

200.7 MET-DIG (CLP) Barium Water 0.6 4

200.7 MET-DIG (CLP) Beryllium Water 0.5 1

200.7 MET-DIG (CLP) Bismuth Water 6 40

200.7 MET-DIG (CLP) Boron Water 4 20

200.7 MET-DIG (CLP) Cadmium Water 0.5 1

200.7 MET-DIG (CLP) Calcium Water 0.9 20

200.7 MET-DIG (CLP) Chromium Water 0.9 4

200.7 MET-DIG (CLP) Cobalt Water 1 2

200.7 MET-DIG (CLP) Copper Water 2 4

200.7 MET-DIG (CLP) Iron Water 3 20

200.7 MET-DIG (CLP) Lead Water 5 10

200.7 MET-DIG (CLP) Lithium Water 4 20

200.7 MET-DIG (CLP) Magnesium Water 0.3 5

200.7 MET-DIG (CLP) Manganese Water 0.3 1

200.7 MET-DIG (CLP) Molybdenum Water 0.9 4

200.7 MET-DIG (CLP) Nickel Water 0.6 4

200.7 MET-DIG (CLP) Phosphorus Water 6 40

200.7 MET-DIG (CLP) Potassium Water 60 200

200.7 MET-DIG (CLP) Selenium Water 9 20

200.7 MET-DIG (CLP) Silicon Water 20 200

200.7 MET-DIG (CLP) Silver Water 2 4

200.7 MET-DIG (CLP) Sodium Water 20 200

200.7 MET-DIG (CLP) Strontium Water 0.2 1

200.7 MET-DIG (CLP) Sulfur Water 20 40

200.7 MET-DIG (CLP) Thallium Water 4 10

200.7 MET-DIG (CLP) Tin Water 3 20

200.7 MET-DIG (CLP) Titanium Water 0.8 2

200.7 MET-DIG (CLP) Vanadium Water 1 4

200.7 MET-DIG (CLP) Zinc Water 0.6 4

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6010C EPA 3050B Aluminum Soil 0.5 2

6010C EPA 3050B Antimony Soil 2 4

6010C EPA 3050B Arsenic Soil 2 4

6010C EPA 3050B Barium Soil 0.3 0.8

6010C EPA 3050B Beryllium Soil 0.08 0.2

6010C EPA 3050B Bismuth Soil 3 8

6010C EPA 3050B Boron Soil 0.7 4

6010C EPA 3050B Cadmium Soil 0.09 0.2

6010C EPA 3050B Calcium Soil 1 4

6010C EPA 3050B Chromium Soil 0.3 0.8

6010C EPA 3050B Cobalt Soil 0.2 0.4

6010C EPA 3050B Copper Soil 0.4 0.8

6010C EPA 3050B Iron Soil 2 4

6010C EPA 3050B Lead Soil 0.7 2

6010C EPA 3050B Lithium Soil 0.6 4

6010C EPA 3050B Magnesium Soil 0.2 2

6010C EPA 3050B Manganese Soil 0.04 0.2

6010C EPA 3050B Molybdenum Soil 0.2 0.8

6010C EPA 3050B Nickel Soil 0.2 0.8

6010C EPA 3050B Phosphorus Soil 3 8

6010C EPA 3050B Potassium Soil 10 40

6010C EPA 3050B Selenium Soil 2 4

6010C EPA 3050B Silver Soil 0.3 0.8

6010C EPA 3050B Sodium Soil 5 40

6010C EPA 3050B Strontium Soil 0.05 0.2

6010C EPA 3050B Sulfur Soil 4 8

6010C EPA 3050B Thallium Soil 0.8 2

6010C EPA 3050B Tin Soil 0.6 4

6010C EPA 3050B Titanium Soil 0.2 0.4

6010C EPA 3050B Vanadium Soil 0.3 0.8

6010C EPA 3050B Zinc Soil 0.2 1

6010C/AVS-SEM EPA 821/R-91-100 Antimony Soil 0.0008 0.003

6010C/AVS-SEM EPA 821/R-91-100 Arsenic Soil 0.002 0.005

6010C/AVS-SEM EPA 821/R-91-100 Cadmium Soil 0.00007 0.0002

6010C/AVS-SEM EPA 821/R-91-100 Chromium Soil 0.0004 0.002

6010C/AVS-SEM EPA 821/R-91-100 Copper Soil 0.0005 0.002

6010C/AVS-SEM EPA 821/R-91-100 Lead Soil 0.0005 0.001

6010C/AVS-SEM EPA 821/R-91-100 Nickel Soil 0.0003 0.001

6010C/AVS-SEM EPA 821/R-91-100 Silver Soil 0.0003 0.001

6010C/AVS-SEM EPA 821/R-91-100 Zinc Soil 0.0003 0.003

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6010C MET-DIG (CLP) Aluminum Water 4 10

6010C MET-DIG (CLP) Antimony Water 6 20

6010C MET-DIG (CLP) Arsenic Water 5 10

6010C MET-DIG (CLP) Barium Water 0.6 4

6010C MET-DIG (CLP) Beryllium Water 0.5 1

6010C MET-DIG (CLP) Bismuth Water 6 40

6010C MET-DIG (CLP) Boron Water 4 20

6010C MET-DIG (CLP) Cadmium Water 0.5 1

6010C MET-DIG (CLP) Calcium Water 0.9 20

6010C MET-DIG (CLP) Chromium Water 0.9 4

6010C MET-DIG (CLP) Cobalt Water 1 2

6010C MET-DIG (CLP) Copper Water 2 4

6010C MET-DIG (CLP) Iron Water 3 20

6010C MET-DIG (CLP) Lead Water 5 10

6010C MET-DIG (CLP) Lithium Water 4 20

6010C MET-DIG (CLP) Magnesium Water 0.3 5

6010C MET-DIG (CLP) Manganese Water 0.3 1

6010C MET-DIG (CLP) Molybdenum Water 0.9 4

6010C MET-DIG (CLP) Nickel Water 0.6 4

6010C MET-DIG (CLP) Phosphorus Water 6 40

6010C MET-DIG (CLP) Potassium Water 60 200

6010C MET-DIG (CLP) Selenium Water 9 20

6010C MET-DIG (CLP) Silicon Water 20 200

6010C MET-DIG (CLP) Silver Water 2 4

6010C MET-DIG (CLP) Sodium Water 20 200

6010C MET-DIG (CLP) Strontium Water 0.2 1

6010C MET-DIG (CLP) Sulfur Water 20 40

6010C MET-DIG (CLP) Thallium Water 4 10

6010C MET-DIG (CLP) Tin Water 3 20

6010C MET-DIG (CLP) Titanium Water 0.8 2

6010C MET-DIG (CLP) Vanadium Water 1 4

6010C MET-DIG (CLP) Zinc Water 0.6 4

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6010C PSEP TISSUE Aluminum Tissue 0.3 1

6010C PSEP TISSUE Antimony Tissue 0.5 2

6010C PSEP TISSUE Arsenic Tissue 0.5 1

6010C PSEP TISSUE Barium Tissue 0.07 0.4

6010C PSEP TISSUE Beryllium Tissue 0.05 0.1

6010C PSEP TISSUE Boron Tissue 0.8 2

6010C PSEP TISSUE Cadmium Tissue 0.04 0.1

6010C PSEP TISSUE Calcium Tissue 2 4

6010C PSEP TISSUE Chromium Tissue 0.08 0.4

6010C PSEP TISSUE Cobalt Tissue 0.07 0.2

6010C PSEP TISSUE Copper Tissue 0.2 0.4

6010C PSEP TISSUE Iron Tissue 1 2

6010C PSEP TISSUE Lead Tissue 0.3 1

6010C PSEP TISSUE Lithium Tissue 0.3 2

6010C PSEP TISSUE Magnesium Tissue 0.6 2

6010C PSEP TISSUE Manganese Tissue 0.03 0.1

6010C PSEP TISSUE Molybdenum Tissue 0.2 0.4

6010C PSEP TISSUE Nickel Tissue 0.2 0.4

6010C PSEP TISSUE Phosphorus Tissue 2 4

6010C PSEP TISSUE Potassium Tissue 9 20

6010C PSEP TISSUE Selenium Tissue 0.9 2

6010C PSEP TISSUE Silicon Tissue 4 20

6010C PSEP TISSUE Silver Tissue 0.2 0.4

6010C PSEP TISSUE Sodium Tissue 2 20

6010C PSEP TISSUE Strontium Tissue 0.04 0.1

6010C PSEP TISSUE Thallium Tissue 0.4 1

6010C PSEP TISSUE Tin Tissue 0.3 2

6010C PSEP TISSUE Titanium Tissue 0.08 0.2

6010C PSEP TISSUE Vanadium Tissue 0.2 0.4

6010C PSEP TISSUE Zinc Tissue 0.2 0.4

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6010C 1311/3010A Antimony TCLP 0.03 0.1

6010C 1311/3010A Arsenic TCLP 0.025 0.05

6010C 1311/3010A Barium TCLP 0.5 1

6010C 1311/3010A Beryllium TCLP 0.001 0.005

6010C 1311/3010A Cadmium TCLP 0.001 0.05

6010C 1311/3010A Chromium TCLP 0.01 0.05

6010C 1311/3010A Cobalt TCLP 0.0035 0.01

6010C 1311/3010A Copper TCLP 0.01 0.1

6010C 1311/3010A Lead TCLP 0.02 0.05

6010C 1311/3010A Manganese TCLP 0.0025 0.005

6010C 1311/3010A Nickel TCLP 0.0035 0.1

6010C 1311/3010A Selenium TCLP 0.025 0.1

6010C 1311/3010A Silver TCLP 0.004 0.05

6010C 1311/3010A Thallium TCLP 0.1 0.25

6010C 1311/3010A Zinc TCLP 0.1 1

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Source Final Final

Analyte Source Concentration Aliquot Volume Concentration

(ppm) (mL) (mL) (ppm)

Antimony (1) 100 5 1000 0.5

Beryllium (1) 100 5 1000 0.5

Boron (1) 100 5 1000 0.5

Cadmium (1) 100 5 1000 0.5

Calcium Ca stock 1000 0.5 1000 1.0*

Chromium (1) 100 5 1000 0.5

Cobalt (1) 100 5 1000 0.5

Copper (1) 100 5 1000 0.5

Iron (1) 100 5 1000 0.5

Lead (1) 100 5 1000 0.5

Magnesium (1) 100 5 1000 0.5

Manganese (1) 100 5 1000 0.5

Molybdenum (1) 100 5 1000 0.5

Nickel (1) 100 5 1000 0.5

Selenium (1) 100 5 1000 0.5

Silver (1) 100 5 1000 0.5

Tin Elemental Stock 1000 0.5 1000 0.5

Thallium (1) 100 5 1000 0.5

Titanium (1) 100 5 1000 0.5

Vanadium (1) 100 5 1000 0.5

Zinc (1) 100 5 1000 0.5

Hydrochloric Acid - - 50 1000 5%

Nitric Acid - - 10 1000 1%

(1) Mixed Standard, QCS-26

* 0.5mL 1000ppm Ca added to 5mL QCS-26(100ppm Ca), 1000mL Final Volume

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ICV1 Solution

Source Final Final



Aluminum QCP-CICV-1 1000 2.5 500 5.0

Antimony QCP-CICV-1 1000 1.25 500 2.5

Arsenic QCP-CICV-3 500 2.5 500 2.5

Barium QCP-CICV-1 1000 2.5 500 5.0

Beryllium QCP-CICV-1 25 2.5 500 0.125

Cadmium QCP-CICV-3 250 2.5 500 1.25

Calcium QCP-CICV-1 2500 2.5 500 12.5

Chromium QCP-CICV-1 100 2.5 500 0.5

Cobalt QCP-CICV-1 250 2.5 500 1.25

Copper QCP-CICV-1 125 2.5 500 0.625

Iron QCP-CICV-1 500 2.5 500 2.5

Lead QCP-CICV-3 500 2.5 500 2.5

Magnesium QCP-CICV-1 2500 2.5 500 12.5

Manganese QCP-CICV-1 250 2.5 500 1.25

Molybdenum Elemental Stock 1000 1.0 500 2.0

Nickel QCP-CICV-1 250 2.5 500 1.25

Potassium QCP-CICV-1 2500 2.5 500 12.5

Selenium QCP-CICV-3 500 2.5 500 2.5

Silver QCP-CICV-1 125 2.5 500 0.625

Sodium QCP-CICV-1 2500 2.5 500 12.5

Thallium QCP-CICV-3 500 2.5 500 2.5

Titanium Elemental Stock 1000 1.0 500 2.0

Vanadium QCP-CICV-1 250 2.5 500 1.25

Zinc QCP-CICV-1 250 2.5 500 1.25


Nitric Acid - - 5 500 1%

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ICSA Solution

Source Final Final



Aluminum CLPP-ICS-A 5000 50 500 500

Calcium CLPP-ICS-A 5000 50 500 500

Iron CLPP-ICS-A 2000 50 500 200

Magnesium CLPP-ICS-A 5000 50 500 500


Nitric Acid - - 5 500 1%

ICSAB Solution

Source Final Final



Aluminum CLPP-ICS-A 5000 50 500 500

Antimony Elemental Stock 1000 0.5 500 1

Barium CLPP-ICS-B 50 5 500 0.5

Beryllium CLPP-ICS-B 50 5 500 0.5

Cadmium CLPP-ICS-B 100 5 500 1

Calcium CLPP-ICS-A 5000 50 500 500

Chromium CLPP-ICS-B 50 5 500 0.5

Cobalt CLPP-ICS-B 50 5 500 0.5

Copper CLPP-ICS-B 50 5 500 0.5

Iron CLPP-ICS-A 2000 50 500 200

Lead CLPP-ICS-B 100 5 500 1

Magnesium CLPP-ICS-A 5000 50 500 500

Manganese CLPP-ICS-B 50 5 500 0.5

Nickel CLPP-ICS-B 100 5 500 1

Silver CLPP-ICS-B 100 5 500 1

Vanadium CLPP-ICS-B 50 5 500 0.5

Zinc CLPP-ICS-B 100 5 500 1

HCl - - 25 500 0.05

HNO3 - - 5 500 0.01

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Analyte Wavelength

Aluminum 237.3

Antimony 206.8

Arsenic 189.0

Barium 233.5

Beryllium 313.0

Boron 249.7

Cadmium 226.5

Calcium 317.9

Calcium 211.2 High Line

Chromium 267.7

Cobalt 228.6

Copper 324.7

Iron 259.9

Iron 271.4 High Line

Lead 220.3

Lithium 670.7

Magnesium 279.5

Magnesium 202.5 High Line

Manganese 257.6

Manganese 293.9 High Line

Molybdenum 202.0

Nickel 231.6

Phosphorus 214.9

Potassium 766.4

Selenium 196.0

Silicon 251.6

Silver 328.0

Sodium 589.5

Strontium 407.7

Thallium 190.8

Tin 189.9

Titanium 323.4

Vanadium 310.2

Zinc 206.2

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Analyte Wavelength

Aluminum 167.0 Low Line

Aluminum 394.4

Antimony 206.8

Antimony 217.5 Alternate

Arsenic 189.0

Barium 455.4

Beryllium 234.8

Boron 249.6

Cadmium 226.5

Cadmium 214.4 Alternate

Calcium 315.8

Calcium 393.3 Low Line

Chromium 267.7

Cobalt 230.7

Cobalt 228.6 Alternate

Copper 327.3

Copper 224.7 Alternate

Iron 259.9

Lead 220.3

Lithium 670.7

Magnesium 279.0 High Line

Magnesium 279.5 Low Line

Magnesium 285.2

Manganese 257.6

Manganese 260.5 High Line

Molybdenum 202.0

Nickel 221.6

Nickel 231.6 Alternate

Phosphorus 214.9

Phosphorus 178.2 Alternate

Potassium 766.4

Selenium 196.0

Silicon 251.6

Silver 328.0

Sodium 588.9 Alternate

Sodium 589.5

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Analyte Wavelength

Strontium 407.7

Thallium 190.8

Tin 189.9

Titanium 336.1

Vanadium 292.4

Zinc 206.2

Zinc 213.8 Alternate

AECOM Environment


Section: Attachment B Revision: 3

Date: May 2015

Attachment B Gamma Spectroscopy Library


AECOM Environment


Section: Attachment C Revision: 3

Date: May 2015

Attachment C Radioisotope Calculation Spreadsheet


EXAMPLE TABLE GAMMA SPECTROSCOPY RESULTS AFTER 28-DAY INGROWTH PERIOD

PINES AREA OF INVESTIGATIONSUPPLEMENTAL SOIL CHARACTERIZATION

Calculated Calculated Calculated Calculated Calculated MeasuredSample I.D. Be-7 Am-241 K-40 Ba-137m Cs-137 (a) Co-60 Tl-208 Pb-210 Bi-212 Pb-212 Bi-214 Pb-214 Ac-228 Ra-228 (b) Ra-226 (c) Total Ra (d) Pa-234m Th-234 U-238 (e) U-235

GS001 1.0 1.0 1.0 1.0 1.1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 1.0 1.0 1.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.00.0 0.0 0.0 0.0

Notes: Equations:(a) Cs-137 = 0.946 x Ba-137m(b) Ra-228 = Ac-228(c) Ra-226 = (Pb-214 + Bi-214) / 2(d) Total Ra = Ra-228 + Ra-226(e) U-238 = (Pa-234m + Th-234) / 2

Measured Measured Measured

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